CN114505081A - Metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier and preparation method thereof - Google Patents
Metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier and preparation method thereof Download PDFInfo
- Publication number
- CN114505081A CN114505081A CN202210238413.8A CN202210238413A CN114505081A CN 114505081 A CN114505081 A CN 114505081A CN 202210238413 A CN202210238413 A CN 202210238413A CN 114505081 A CN114505081 A CN 114505081A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- sulfur
- reduced graphene
- catalyst carrier
- molybdenum disulfide
- 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.)
- Pending
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 160
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 75
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- 239000000017 hydrogel Substances 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 239000004964 aerogel Substances 0.000 claims abstract description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 2
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 230000007774 longterm Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000004873 anchoring Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- -1 tungsten carbide) Chemical class 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- 241000446313 Lamella Species 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Images
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/23—
-
- B01J35/33—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier and a preparation method thereof, wherein the preparation method comprises the steps of preparing a graphene oxide dispersion solution, a sulfur-doped reduced graphene oxide hydrogel and a sulfur-doped reduced graphene oxide aerogel in sequence, and then mixing the aerogel with a sulfur source and a molybdenum source at 150-180 ℃ for reaction to obtain the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier. According to the preparation method, the anchoring effect of the reduced graphene oxide on the molybdenum disulfide is improved through sulfur doping, the molybdenum disulfide exists in a metal phase instead of a conventional 2H phase, the high conductivity of the catalyst carrier is ensured, the oxidation resistance of the catalyst carrier is enhanced through the introduction of the metal phase molybdenum disulfide and sulfur elements, the long-term stability of the catalyst carrier is greatly improved, and the composite catalyst carrier also has the advantages of large specific surface area, high catalytic activity and the like, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier and a preparation method thereof.
Background
Carbon black is a common carrier of platinum carbon catalysts used for cathodes of energy devices such as fuel cells, metal-air cells and the like. Although current commercial carbon blacks have the advantages of large specific surface area, low cost, high conductivity, etc., their low platinum loading and poor durability become key factors that limit the commercialization of fuel cells and metal-air cells. In addition, in the long-term use process of the battery, the platinum particles are easy to generate an Ostwald curing process to overgrow, so that the catalytic performance of the platinum particles is reduced; meanwhile, in a highly oxidative operating environment inside the battery, the shedding of platinum particles caused indirectly by the corrosion of carbon black becomes the biggest obstacle to maintaining the stability of the platinum-carbon catalyst in the battery.
Graphene is a carbon material with high conductivity and strong stability, but the chemical inertness thereof makes platinum and other noble metal nanocrystals difficult to load. The surface of the graphene oxide has an oxygen-rich functional group, and the application of the graphene oxide in the field of batteries is a feasible method for improving the loading amount and the utilization rate of noble metals, however, compared with a complete graphene structure, a large number of defects exist in the graphene oxide, so that the graphene oxide serving as a battery catalyst carrier has the defects of poor durability and the like. To this end, researchers have proposed that graphene oxide be composited with conductive polymers (e.g., polyaniline), metal oxides (e.g., titanium dioxide, tungsten trioxide), carbides (e.g., tungsten carbide), nitrides (e.g., molybdenum nitride), and sulfides (e.g., molybdenum disulfide) to maintain the stability of the catalyst support for the battery. Among them, molybdenum disulfide has become a focus of attention for a novel battery catalyst carrier due to its high electrocatalytic activity and stability in a transition metal sulfide family.
Anwar et al [ Chinese Journal of Catalysis 40(2019)1160-1167] discloses a molybdenum disulfide-graphene catalyst loaded with platinum particles, a molybdenum disulfide-graphene composite material is obtained by carrying out hydrothermal reaction on graphene oxide and ammonium thiomolybdate, and platinum nanocrystals are grown by an ethylene glycol reduction method under an alkaline condition. The loss of the electrochemical area of the catalyst after 10000 cycles of accelerated cycle test in the oxygen reduction catalytic reaction is 46.2 percent, which is less than 57.6 percent of the loss of commercial platinum carbon, and shows that the stability of the catalyst carrier is enhanced.
Ramakrishnan et al ACS appl. mater. interfaces 2019,11, 12504-.
Chinese patent document with publication number CN104409706B discloses a molybdenum disulfide/sulfur and nitrogen doped graphene nanosheet composite material and a preparation method and application thereof, wherein ammonium tetrathiomolybdate, graphene oxide and thiourea are dissolved in N, N-dimethylformamide and uniformly mixed to obtain a mixed solution, then the mixed solution is dried and finally sintered in protective gas to obtain the composite material; in this patent document, the particle size of graphene is reduced, and the composite material has the characteristics of atom doping modification and a large specific surface area.
However, the above-described conventional catalyst carrier still has the following problems: due to the low conductivity of the molybdenum disulfide and the easy stacking property of the lamella, the activity of the catalyst carrier is influenced to a great extent, and the reinforcing effect of the molybdenum disulfide on the stability of the catalyst carrier cannot be exerted. Therefore, it is urgent to research on how to overcome the above technical problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, particularly aims at overcoming the defects of poor oxidation resistance, low long-term stability, poor conductivity of a molybdenum disulfide catalyst carrier and the like of the prior noble metal catalyst carrier, and provides a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier which is large in specific surface area, high in catalytic activity, high in conductivity and long-term stability and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme.
A preparation method of a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier comprises the following steps:
s1, mixing and dispersing graphene oxide, water, a reducing agent and a sulfur-containing compound to obtain a graphene oxide dispersion liquid;
s2, carrying out hydrothermal reaction on the graphene oxide dispersion liquid obtained in the step S1 at 150-220 ℃ to obtain sulfur-doped reduced graphene oxide hydrogel;
s3, carrying out reduction reaction on the sulfur-doped reduced graphene oxide hydrogel obtained in the step S2 at 600-1000 ℃ in an inert atmosphere to obtain sulfur-doped reduced graphene oxide aerogel;
s4, dispersing a sulfur source and a molybdenum source in water, adding the sulfur-doped reduced graphene oxide aerogel obtained in the step S3, reacting at the temperature of 150-180 ℃, and drying after the reaction to obtain the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier.
In the preparation method of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier, preferably, in step S1, the mass-to-volume ratio of the graphene oxide to water is 1 mg-3 mg: 1 mL.
In the above preparation method of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier, preferably, in step S1, the sulfur-containing compound includes one or more of sulfur powder, concentrated sulfuric acid, dimethyl sulfoxide, thioacetamide and dibenzyl disulfide, and the reducing agent includes one or more of ascorbic acid, citric acid, sodium citrate and oxalic acid.
Preferably, in the step S1, the concentration of sulfur in the graphene oxide dispersion liquid is 0.05mmol/mL to 2.5mmol/mL, and the mass ratio of the reducing agent to the graphene oxide is 2-8: 1. When the sulfur-containing compound is concentrated sulfuric acid, the volume-mass ratio of the concentrated sulfuric acid to the graphene oxide in the step S1 is 20-300 muL: 20-120 mg, the mass fraction of the concentrated sulfuric acid is preferably 98%, and the concentrated sulfuric acid plays a role in doping sulfur.
Preferably, in step S4, the sulfur source includes one or more of potassium thiocyanate, thiourea and sulfur powder, the molybdenum source includes one or more of ammonium molybdate, ammonium paramolybdate, sodium molybdate and molybdenum chloride, a molar ratio of sulfur element in the sulfur source to molybdenum element in the molybdenum source is 2-6: 1, and a mass ratio of the molybdenum source to graphene oxide in step S1 is 10-40: 1.
Preferably, in the step S1, the specific mixing process in the preparation method of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier is as follows: ultrasonically dispersing graphene oxide in water, adding a reducing agent and a sulfur-containing compound, and continuing to ultrasonically disperse to obtain a graphene oxide dispersion liquid; the time of ultrasonic dispersion and the time of continuous ultrasonic dispersion are both 1 h-6 h.
In the preparation method of the metal-phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier, preferably, in step S2, the hydrothermal reaction time is 6 to 24 hours.
Preferably, in step S3, the reduction reaction time is 1 to 3 hours, the sulfur-doped reduced graphene oxide hydrogel is cleaned and dried before use, the cleaning is performed with water, the drying is freeze drying, rotary evaporation or vacuum drying, the vacuum drying temperature is 60 to 80 ℃, the flow rate of the inert atmosphere is 50 to 150sccm, and the inert atmosphere is argon gas.
Preferably, in the step S4, the reaction time is 18 to 48 hours, the drying is freeze drying, rotary evaporation or vacuum drying, and the vacuum drying temperature is 60 to 80 ℃.
As a general technical concept, the invention also provides a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier prepared by the preparation method.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a preparation method of a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier, which is characterized in that sulfur atoms are introduced into graphene oxide through a sulfur-containing compound, and then the anchoring effect of the reduced graphene oxide on a sulfur source and a molybdenum source is improved through sulfur doping, so that a metal phase molybdenum disulfide layer vertically grows on the reduced graphene oxide layer and is not stacked, the utilization rate of the metal phase molybdenum disulfide in the catalyst carrier is improved, and the catalytic activity of the catalyst carrier is further improved; meanwhile, the sulfur-doped reduced graphene oxide exists in an aerogel form, so that the specific surface area of the catalyst carrier is enlarged, the mass transfer efficiency of the catalyst carrier is improved, and the activity of the catalyst carrier is further improved; then, mixing the sulfur-doped reduced graphene oxide aerogel with a sulfur source and a molybdenum source precursor solution at the temperature of 150-180 ℃ for reaction, so that molybdenum disulfide exists in a metal phase instead of a conventional 2H phase, and the high conductivity of the catalyst carrier is ensured. The preparation method has the advantages of simple process, low cost and the like, and is beneficial to industrial application.
(2) In the preparation method, the mass-to-volume ratio of the graphene oxide to the water is 1 mg-3 mg: 1mL, and the sulfur-doped reduced graphene oxide hydrogel is obtained by optimizing the mass-to-volume ratio of the graphene oxide to the water, so that excessive accumulation among sheets caused by overhigh concentration of the graphene oxide is avoided, and the formation of an aerogel structure is ensured.
(3) The metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier is in an aerogel shape, and the reduced graphene oxide lamella layers are not stacked mutually, so that the mass transfer efficiency and the loading efficiency of noble metals are improved; the metal phase molybdenum disulfide lamella grows on the reduction-oxidation graphene lamella vertically and is not stacked, the utilization rate of the metal phase molybdenum disulfide in the catalyst carrier is improved, the molybdenum disulfide exists in a metal phase instead of a conventional 2H phase, the high conductivity of the catalyst carrier is ensured, and meanwhile, the density of active sites is improved due to the fact that the number of coordination unsaturated atoms on the surface of the molybdenum disulfide is increased, and the excellent catalytic activity of the catalyst carrier is further ensured. Compared with the prior art, the synergistic effect of the metal phase molybdenum disulfide and the noble metal in the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier enables the metal phase molybdenum disulfide to be more firmly loaded on the catalyst carrier without falling off, and the oxidation resistance of the catalyst carrier is enhanced by introducing the metal phase molybdenum disulfide and sulfur elements, so that the long-term stability of the catalyst carrier is greatly improved. The metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier has the advantages of large specific surface area, high catalytic activity, high conductivity, long-term stability and the like, and has a good application prospect.
Drawings
Fig. 1 is a diagram of a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst support prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst support prepared in example 1 of the present invention.
Fig. 3 is a TEM image of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst support prepared in example 1 of the present invention.
Fig. 4 is a diagram of an X-ray photoelectron spectroscopy analysis of molybdenum element of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier prepared in example 1 of the present invention.
Fig. 5 is a cyclic voltammetry curve diagram of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier prepared in example 1 of the present invention.
Fig. 6 is a circular polarization curve diagram of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier prepared in example 1 of the present invention.
Fig. 7 is an SEM image of the metallic phase layered molybdenum disulfide/reduced graphene oxide composite catalyst support prepared in comparative example 1.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. The materials and equipment used in the following examples are commercially available.
Example 1:
the invention discloses a preparation method of a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier, which comprises the following steps:
(1) weighing 60mg of graphene oxide sheets, dispersing the graphene oxide sheets in 30mL of deionized water, performing ultrasonic dispersion for 1h, sequentially adding 300 mu L of concentrated sulfuric acid (98 wt%) and 250mg of citric acid, and continuing to perform ultrasonic dispersion for 1h to obtain a graphene oxide dispersion liquid, wherein the content of sulfur element in the graphene oxide dispersion liquid is 1.8 mmol/mL.
(2) And transferring the graphene oxide dispersion liquid into a 50mL polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 12h at the temperature of 180 ℃ to obtain the sulfur-doped reduced graphene oxide hydrogel.
(3) And (2) cleaning the sulfur-doped reduced graphene oxide hydrogel with water, freezing the sulfur-doped reduced graphene oxide hydrogel by using liquid nitrogen, drying the frozen sulfur-doped reduced graphene oxide hydrogel in a freeze dryer for 48 hours, then placing the frozen sulfur-doped reduced graphene oxide hydrogel in a tubular furnace, and treating the frozen sulfur-doped reduced graphene oxide hydrogel at 800 ℃ for 3 hours under the protection of argon gas at the flow rate of 100sccm to obtain the sulfur-doped reduced graphene oxide aerogel.
(4) Weighing 2.5g of thiourea and 1.2g of ammonium molybdate, dispersing in 40mL of deionized water, ultrasonically dispersing for 1h, transferring to a 100mL polytetrafluoroethylene reaction kettle, adding the sulfur-doped reduced graphene oxide aerogel, reacting at 180 ℃ for 24h, then separating to obtain a reaction product, freezing the reaction product by using liquid nitrogen, and drying in a freeze dryer for 48h to obtain the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier, wherein the catalyst carrier is in an aerogel-like structure in a macroscopic view, the height is about 14mm, and the diameter is about 6mm, as shown in FIG. 1.
Fig. 2 is an SEM image of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst support prepared in example 1 of the present invention, and fig. 3 is a TEM image of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst support prepared in example 1 of the present invention, and it can be seen from fig. 2 and fig. 3 that the reduced graphene oxide sheets are not stacked inside the aerogel, and the metal phase molybdenum disulfide sheet layer is vertically grown on the reduced graphene oxide sheet layer.
Fig. 4 is a diagram of an X-ray photoelectron spectroscopy analysis of molybdenum element of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier prepared in example 1 of the present invention. As can be seen from FIG. 4, the 3/2 and 5/2 peaks of Mo 3d in the X-ray photoelectron spectrum are at the positions of 231.7 and 228.5eV, respectively, corresponding to the metal phase MoS2The presence of molybdenum disulfide in the form of a metallic phase is demonstrated.
The cyclic voltammetry curve and polarization curve of the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier prepared in embodiment 1 of the present invention before and after 30000 accelerated cyclic oxygen reduction tests are tested by using national standard GB/T20042.4-2009, as shown in fig. 5 and 6. As can be seen from fig. 5 and 6, the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier has no obvious performance attenuation and shows good long-term stability in a 30000-time cyclic oxygen reduction test.
Comparative example 1:
a preparation method of a metal phase molybdenum disulfide/reduced graphene oxide composite catalyst carrier is basically the same as that in example 1, and the difference is only that: in the step (1), concentrated sulfuric acid is not added.
Fig. 7 is an SEM image of the metal phase molybdenum disulfide/reduced graphene oxide composite catalyst support prepared in comparative example 1. As can be seen from fig. 7, in the metal phase molybdenum disulfide/reduced graphene oxide composite catalyst carrier prepared in comparative example 1, a large number of molybdenum disulfide nanoflowers are inserted between reduced graphene oxide lamella, and do not grow on the reduced graphene oxide lamella, so that it can be proved that the anchoring effect of the reduced graphene oxide on molybdenum disulfide can be effectively improved by doping sulfur element.
Example 2:
the invention discloses a preparation method of a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier, which comprises the following steps:
(1) weighing 40mg of graphene oxide sheets, dispersing in 30mL of deionized water, performing ultrasonic dispersion for 1h, sequentially adding 150 mu L of dimethyl sulfoxide and 250mg of ascorbic acid, and continuing to perform ultrasonic dispersion for 1h to obtain a graphene oxide dispersion liquid, wherein the content of sulfur in the graphene oxide dispersion liquid is 0.07 mmol/mL.
(2) And transferring the graphene oxide dispersion liquid into a 50mL polytetrafluoroethylene reaction kettle, and reacting at 180 ℃ for 24h to obtain the sulfur-doped reduced graphene oxide hydrogel.
(3) And (2) cleaning the sulfur-doped reduced graphene oxide hydrogel with water, then carrying out vacuum drying treatment at the temperature of 80 ℃, then placing the cleaned sulfur-doped reduced graphene oxide hydrogel into a tubular furnace, and treating the cleaned sulfur-doped reduced graphene oxide hydrogel for 1h at the temperature of 900 ℃ under the protection of argon gas at the flow rate of 50sccm to obtain the sulfur-doped reduced graphene oxide aerogel.
(4) Weighing 3g of thiourea and 1.5g of sodium molybdate, dispersing in 50mL of deionized water, ultrasonically dispersing for 1h, transferring to a 100mL polytetrafluoroethylene reaction kettle, adding the sulfur-doped reduced graphene oxide aerogel, reacting at 160 ℃ for 36h, separating to obtain a reaction product, freezing the reaction product by using liquid nitrogen, and drying in a freeze dryer for 48h to obtain the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier.
Example 3:
the invention discloses a preparation method of a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier, which comprises the following steps:
(1) weighing 80mg of graphene oxide sheets, dispersing the graphene oxide sheets in 30mL of deionized water, performing ultrasonic dispersion for 1h, sequentially adding 100mg of sulfur powder and 200mg of sodium citrate, and continuing to perform ultrasonic dispersion for 1h to obtain a graphene oxide dispersion liquid, wherein the content of sulfur in the graphene oxide dispersion liquid is 0.05 mmol/mL.
(2) And transferring the graphene oxide dispersion liquid into a 50mL polytetrafluoroethylene reaction kettle, and reacting at the temperature of 200 ℃ for 18h to obtain the sulfur-doped reduced graphene oxide hydrogel.
(3) And (3) cleaning the sulfur-doped reduced graphene oxide hydrogel with water, drying the cleaned sulfur-doped reduced graphene oxide hydrogel by using a rotary evaporator, then placing the dried sulfur-doped reduced graphene oxide hydrogel into a tubular furnace, and treating the dried sulfur-doped reduced graphene oxide hydrogel for 2 hours at 700 ℃ under the protection of argon gas at the flow rate of 150sccm to obtain the sulfur-doped reduced graphene oxide aerogel.
(4) Weighing 2.1g of thiourea and 0.9g of ammonium paramolybdate, dispersing in 35mL of deionized water, ultrasonically dispersing for 1h, transferring to a 100mL polytetrafluoroethylene reaction kettle, adding the sulfur-doped reduced graphene oxide aerogel, reacting at the temperature of 150 ℃ for 18h, separating to obtain a reaction product, and drying the reaction product in a vacuum drying oven at the temperature of 70 ℃ to obtain the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier.
Example 4:
the invention discloses a preparation method of a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier, which comprises the following steps:
(1) weighing 90mg of graphene oxide sheets, dispersing the graphene oxide sheets in 30mL of deionized water, performing ultrasonic dispersion for 1h, sequentially adding 150mg of thioacetamide and 180mg of oxalic acid, and continuing to perform ultrasonic dispersion for 3h to obtain a graphene oxide dispersion liquid, wherein the content of sulfur element in the graphene oxide dispersion liquid is 0.066 mmol/mL.
(2) And transferring the graphene oxide dispersion liquid into a 50mL polytetrafluoroethylene reaction kettle, and reacting at 160 ℃ for 20h to obtain the sulfur-doped reduced graphene oxide hydrogel.
(3) And (2) cleaning the sulfur-doped reduced graphene oxide hydrogel with water, freezing the sulfur-doped reduced graphene oxide hydrogel by using liquid nitrogen, drying the frozen sulfur-doped reduced graphene oxide hydrogel in a freeze dryer for 60 hours, then placing the frozen sulfur-doped reduced graphene oxide hydrogel in a tubular furnace, and treating the frozen sulfur-doped reduced graphene oxide hydrogel at 700 ℃ for 1.5 hours under the protection of argon gas at the flow rate of 100sccm to obtain the sulfur-doped reduced graphene oxide aerogel.
(4) Weighing 2.3g of thiourea and 1.5g of molybdenum chloride, dispersing in 45mL of deionized water, ultrasonically dispersing for 2h, transferring to a 100mL polytetrafluoroethylene reaction kettle, adding the sulfur-doped reduced graphene oxide aerogel, reacting at 170 ℃ for 48h, separating to obtain a reaction product, and drying the reaction product by using a rotary evaporator to obtain the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (10)
1. A preparation method of a metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier is characterized by comprising the following steps:
s1, mixing and dispersing graphene oxide, water, a reducing agent and a sulfur-containing compound to obtain a graphene oxide dispersion liquid;
s2, carrying out hydrothermal reaction on the graphene oxide dispersion liquid obtained in the step S1 at 150-220 ℃ to obtain sulfur-doped reduced graphene oxide hydrogel;
s3, carrying out reduction reaction on the sulfur-doped reduced graphene oxide hydrogel obtained in the step S2 at 600-1000 ℃ in an inert atmosphere to obtain sulfur-doped reduced graphene oxide aerogel;
s4, dispersing a sulfur source and a molybdenum source in water, adding the sulfur-doped reduced graphene oxide aerogel obtained in the step S3, reacting at the temperature of 150-180 ℃, and drying after the reaction to obtain the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier.
2. The method for preparing the metal-phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier according to claim 1, wherein in step S1, the mass-to-volume ratio of the graphene oxide to water is 1 mg-3 mg: 1 mL.
3. The method for preparing a metal-phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier according to claim 1, wherein in step S1, the sulfur-containing compound comprises one or more of sulfur powder, concentrated sulfuric acid, dimethyl sulfoxide, thioacetamide and dibenzyl disulfide, and the reducing agent comprises one or more of ascorbic acid, citric acid, sodium citrate and oxalic acid.
4. The method for preparing the metal-phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier according to claim 1, wherein in step S1, the concentration of sulfur in the graphene oxide dispersion liquid is 0.05mmol/mL to 2.5mmol/mL, and the mass ratio of the reducing agent to the graphene oxide is 2-8: 1.
5. The method for preparing the metal-phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier according to claim 1, wherein in step S4, the sulfur source comprises one or more of potassium thiocyanate, thiourea and sulfur powder, the molybdenum source comprises one or more of ammonium molybdate, ammonium paramolybdate, sodium molybdate and molybdenum chloride, the molar ratio of sulfur element in the sulfur source to molybdenum element in the molybdenum source is 2-6: 1, and the mass ratio of the molybdenum source to graphene oxide in step S1 is 10-40: 1.
6. The method for preparing the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier according to any one of claims 1 to 5, wherein in step S1, the specific mixing process is as follows: ultrasonically dispersing graphene oxide in water, adding a reducing agent and a sulfur-containing compound, and continuing to ultrasonically disperse to obtain a graphene oxide dispersion liquid; the time of ultrasonic dispersion and the time of continuous ultrasonic dispersion are both 1 h-6 h.
7. The method for preparing the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier according to any one of claims 1 to 5, wherein in step S2, the hydrothermal reaction time is 6 to 24 hours.
8. The method for preparing the metal-phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier according to any one of claims 1 to 5, wherein in step S3, the reduction reaction time is 1 to 3 hours, the sulfur-doped reduced graphene oxide hydrogel is cleaned and dried before use, the cleaning is performed with water, the drying is freeze drying, rotary evaporation or vacuum drying, the temperature of the vacuum drying is 60 to 80 ℃, the flow rate of the inert atmosphere is 50 to 150sccm, and the inert atmosphere is argon.
9. The method for preparing the metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier according to any one of claims 1 to 5, wherein in the step S4, the reaction time is 18-48 h, the drying is freeze drying, rotary evaporation or vacuum drying, and the temperature of the vacuum drying is 60-80 ℃.
10. The metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier prepared by the preparation method of any one of claims 1 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210238413.8A CN114505081A (en) | 2022-03-10 | 2022-03-10 | Metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210238413.8A CN114505081A (en) | 2022-03-10 | 2022-03-10 | Metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114505081A true CN114505081A (en) | 2022-05-17 |
Family
ID=81553338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210238413.8A Pending CN114505081A (en) | 2022-03-10 | 2022-03-10 | Metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114505081A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115090226A (en) * | 2022-05-24 | 2022-09-23 | 哈尔滨工业大学 | Cobalt-aluminum-doped molybdenum disulfide reduced graphene oxide aerogel, preparation method thereof and application thereof in uranium extraction from seawater |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106057471A (en) * | 2016-05-27 | 2016-10-26 | 同济大学 | Preparation method and application of three-dimensional graphene aerogel load molybdenum disulfide nano-sheet hybridization material |
CN106207125A (en) * | 2016-08-23 | 2016-12-07 | 东华大学 | Sulfur doping selenizing molybdenum/Graphene graphene nanobelt aeroge and preparation thereof |
CN108404936A (en) * | 2018-03-19 | 2018-08-17 | 新疆大学 | A kind of hydro-thermal method synthesis 1T phases molybdenum disulfide/graphene nanocomposite material |
CN108807835A (en) * | 2017-04-28 | 2018-11-13 | 福建新峰二维材料科技有限公司 | The preparation method and battery of one type of metal graphene negative material |
CN109158059A (en) * | 2018-09-29 | 2019-01-08 | 天津理工大学 | One-step method prepares molybdenum disulfide nano bouquet/redox graphene composite aerogel method |
-
2022
- 2022-03-10 CN CN202210238413.8A patent/CN114505081A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106057471A (en) * | 2016-05-27 | 2016-10-26 | 同济大学 | Preparation method and application of three-dimensional graphene aerogel load molybdenum disulfide nano-sheet hybridization material |
CN106207125A (en) * | 2016-08-23 | 2016-12-07 | 东华大学 | Sulfur doping selenizing molybdenum/Graphene graphene nanobelt aeroge and preparation thereof |
CN108807835A (en) * | 2017-04-28 | 2018-11-13 | 福建新峰二维材料科技有限公司 | The preparation method and battery of one type of metal graphene negative material |
CN108404936A (en) * | 2018-03-19 | 2018-08-17 | 新疆大学 | A kind of hydro-thermal method synthesis 1T phases molybdenum disulfide/graphene nanocomposite material |
CN109158059A (en) * | 2018-09-29 | 2019-01-08 | 天津理工大学 | One-step method prepares molybdenum disulfide nano bouquet/redox graphene composite aerogel method |
Non-Patent Citations (1)
Title |
---|
ANTONIA KAGKOURA ET AL: "Sulfur-doped graphene/transition metal dichalcogenide heterostructured hybrids with electrocatalytic activity toward the hydrogen evolution reaction", NANOSCALE ADVANCES * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115090226A (en) * | 2022-05-24 | 2022-09-23 | 哈尔滨工业大学 | Cobalt-aluminum-doped molybdenum disulfide reduced graphene oxide aerogel, preparation method thereof and application thereof in uranium extraction from seawater |
CN115090226B (en) * | 2022-05-24 | 2023-02-10 | 哈尔滨工业大学 | Cobalt-aluminum-molybdenum disulfide-doped reduced graphene oxide aerogel, preparation method thereof and application thereof in extracting uranium from seawater |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112005413B (en) | ZIF-8-based nickel-iron-nitrogen-doped carbon material three-function electrocatalyst and preparation method and application thereof | |
CN109019602B (en) | Molybdenum carbide material, molybdenum carbide @ molybdenum sulfide composite material, and preparation method and application thereof | |
CN107747106B (en) | Nitrogen and sulfur doped three-dimensional carbon nano network loaded molybdenum disulfide nano material and preparation | |
CN109267092B (en) | Molybdenum disulfide composite material and preparation method and application thereof | |
CN112103520B (en) | Anode catalyst of alcohol fuel cell | |
CN110876946B (en) | MoS 2 -RGO-NiO @ Ni foam composite photoelectrocatalysis hydrogen evolution material and preparation method thereof | |
CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
CN113471452B (en) | Multi-site composite nanotube for hydrogen and oxygen evolution reduction and preparation method and application thereof | |
CN111569919B (en) | Molybdenum disulfide quantum dot modified molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution | |
CN111558387A (en) | Molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution | |
CN110787824A (en) | Preparation method and application of vanadium-doped transition metal nitride | |
CN111617780A (en) | Nitrogen-doped nickel-molybdenum-based composite sulfide for stably producing hydrogen by electrolyzing water and preparation method | |
Pan et al. | Carbon-encapsulated Co3V decorated Co2VO4 nanosheets for enhanced urea oxidation and hydrogen evolution reaction | |
CN114505081A (en) | Metal phase layered molybdenum disulfide/reduced graphene oxide composite catalyst carrier and preparation method thereof | |
Chen et al. | Carbon monoxide-resistant copper-cobalt nanocrystal@ nitrogen-doped carbon electrocatalysts for methanol oxidation reaction | |
CN109888314B (en) | Preparation method of boron-cobalt-nitrogen doped carbon nanomaterial for zinc-air battery | |
Zhang et al. | Graphene oxide-wrapped cobalt-doped oxygen-deficient titanium dioxide hollow spheres clusters as efficient sulfur immobilizers for lithium-sulfur batteries | |
Li et al. | Porous direct Z-scheme heterostructures of S-deficient CoS/CdS hexagonal nanoplates for robust photocatalytic H 2 generation | |
Jinyu et al. | Architecture of porous CoS1. 097-C composite nanowire for efficient oxygen reduction reaction | |
CN112076763B (en) | Ni/Ni3S2Nanocluster-graphene composite material and preparation method and application thereof | |
Xu et al. | Hierarchically structured Mo1–2C/Co-encased carbon nanotubes with multi-component synergy as bifunctional oxygen electrocatalyst for rechargeable Zn-air battery | |
CN113502498A (en) | Porous spherical carbon-coated cobalt/tungsten carbide composite loaded on carbon spheres as well as preparation and application thereof | |
Wang et al. | Electrocatalytic performance of Ni-promoted Co nanoclusters supported by N-doped carbon foams for rechargeable Zn-air batteries | |
CN111514912A (en) | Three-dimensional Co-doped WP2Nanosheet array electrocatalyst and preparation method thereof | |
CN115896858B (en) | Double-phase multi-component composite electrocatalytic material 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 |