CN110694693A - Carbon cloth loaded MoSx/UiO-66 composite material, preparation method and application - Google Patents
Carbon cloth loaded MoSx/UiO-66 composite material, preparation method and application Download PDFInfo
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- CN110694693A CN110694693A CN201910853460.1A CN201910853460A CN110694693A CN 110694693 A CN110694693 A CN 110694693A CN 201910853460 A CN201910853460 A CN 201910853460A CN 110694693 A CN110694693 A CN 110694693A
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- carbon cloth
- uio
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- composite material
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 84
- 239000013207 UiO-66 Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000004744 fabric Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910003185 MoSx Inorganic materials 0.000 title claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000001257 hydrogen Substances 0.000 claims abstract description 66
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 66
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 239000011593 sulfur Substances 0.000 claims abstract description 7
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- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims abstract description 4
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- -1 zirconium ions Chemical class 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 10
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 8
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
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- 239000000203 mixture Substances 0.000 claims description 4
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- 238000001514 detection method Methods 0.000 claims description 2
- RXHMDIUZIJSGAI-UHFFFAOYSA-J n,n-dimethylcarbamodithioate;molybdenum(4+) Chemical compound [Mo+4].CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S RXHMDIUZIJSGAI-UHFFFAOYSA-J 0.000 claims description 2
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- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
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- TZOSCSXHFPKRBH-UHFFFAOYSA-N 5-[3-(3,5-dicarboxyphenyl)phenyl]benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C(O)=O)C(O)=O)=C1 TZOSCSXHFPKRBH-UHFFFAOYSA-N 0.000 description 1
- 235000005881 Calendula officinalis Nutrition 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B01J35/33—
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a carbon cloth loaded MoSxThe preparation method and the application of the/UiO-66 composite material comprise the following steps: s1: dissolving an inorganic metal zirconium ion precursor, terephthalic acid and a sulfur-containing molybdenum source precursor into an organic solvent, carrying out ultrasonic treatment, and uniformly mixing to obtain a precursor reaction solution; s2: treating the carbon cloth with an organic solvent, ethanol, deionized water and acid to remove surface impurities; s3: transferring the precursor reaction solution into a reaction container, putting the carbon cloth into the reaction container, carrying out closed reaction at high temperature and high pressure, after the reaction is finished, relieving the pressure to normal pressure, naturally cooling to room temperature, cleaning and drying to obtain the MoS loaded by the carbon clothxa/UiO-66 composite material. The carbon cloth-loaded MoS prepared by the inventionxthe/UiO-66 electro-catalysis composite material shows good performance advantages in the research of electro-catalysis hydrogen production, can be applied to the field of hydrogen production by electrolyzing water, and is a powerful candidate material of an electro-catalysis hydrogen production catalyst. Has great potential and industrial application value in the electrochemical field.
Description
Technical Field
The invention belongs to the technical field of organic-inorganic functional materials and electrochemical energy, in particular to a composite material consisting of a conductive carbon material, an inorganic material and a metal organic framework material, a preparation method and application thereof, and particularly relates to carbon cloth loaded MoSxa/UiO-66 composite material, a preparation method and application thereof.
Background
Hydrogen energy has attracted considerable interest as a sustainable energy source because it has the potential to reduce the heavy dependence on fossil fuels and to reduce carbon dioxide emissions. Electrolysis of water is an efficient, clean technique that can produce high purity hydrogen. As a half reaction of water electrolysis, a hydrogen evolution reaction requires a highly active and stable catalyst.
At present, Pt group metals and their alloys are the best electrocatalysts to drive the electrochemical Hydrogen Evolution Reaction (HER) with very small overpotentials, but their scarcity and high cost have prevented their widespread use. Therefore, the search and development of materials with high electrocatalytic hydrogen production (HER) activity, excellent stability, low cost and abundant reserves are receiving much attention.
To overcome this drawback, many researchers have studied different preparation methods, different materials and modification means, and many low-cost and abundant catalysts, such as transition metal sulfides, carbides, phosphides and nitrides, have been used as electrocatalysts for HER. Among these materials, molybdenum sulfide has become a powerful alternative to Pt group metals because its hydrogen adsorption free energy is close to that of Pt group metals.
As the Metal Organic Frameworks (MOFs) are a novel porous material with extremely large surface area, the metal organic frameworks have regularity of pore space and adjustability of pore diameter and pore surface property. Recently, some MOFs and MOFs based composites have been demonstrated to be useful for oxygen reduction reactions, hydrogen evolution reactions, CO2And electro-oxidation reaction of methanol and ethanol. However, the stability of MOFs has been considered to be a major factor affecting electrochemical performance.
In recent years, various transition metal sulfides, carbides, phosphides and nitrides and metal organic framework materials are widely applied to electrocatalytic hydrogen production research.
CN108118362A discloses a molybdenum disulfide electrocatalytic hydrogen production electrode and a preparation method and application thereof, wherein a cobalt salt, a nickel salt and hexamethylenetetramine are dissolved in methanol to obtain a mixed solution, an electrode substrate is soaked in the mixed solution and reacts for 12 hours at 180 ℃ under a sealed condition to obtain the electrode substrate deposited with a Ni-Co layered double-metal hydroxide nanosheet array. And then dissolving ammonium tetrathiomolybdate in N, N-dimethylformamide, adding a reducing agent, reacting with an electrode substrate of a double-metal hydroxide nanosheet array for 8 hours by heating to 150 ℃ under a sealed condition, washing and drying to obtain the molybdenum disulfide electrocatalytic hydrogen production electrode. The material has a multi-level nanosheet array structure and a large electrochemical active surface area, greatly improves the catalytic activity of molybdenum disulfide, and shows excellent electro-catalytic hydrogen production performance. Layered double hydroxides are deposited on the electrode substrate by a hydrothermal method, molybdenum disulfide with a multi-level structure is obtained, and element doping and structure optimization are realized.
CN105826573A discloses a surface treatment method for improving electrocatalytic hydrogen production performance, firstly, chloride (nickel chloride, cobalt chloride) and hexamethylenetetramine or urea are dissolved in deionized water, a precursor is prepared from a treated nickel foam sheet by a hydrothermal growth method, sodium dihydrogen hypophosphite powder is used as a phosphorus source, the prepared precursor is cut and then put into a quartz tube with one end sealed, high-temperature calcination is carried out in a program-controlled tube furnace by taking nitrogen as protective gas, and finally, the surface treatment method is characterized in thatAnd cleaning and drying the obtained phosphating product by using deionized water to obtain the phosphorus-containing nanosheet or the phosphorus-containing nanowire. And further performing CV cyclic scanning by taking the phosphorus-containing nanosheets or the phosphorus-containing nanowires as working electrodes, a saturated Ag/AgCl electrode as a reference electrode and a platinum sheet as a counter electrode in a three-electrode system, wherein the surface roughness and the surface active sites of the phosphorus-containing nanosheets or the phosphorus-containing nanowires are increased after scanning. Ni2After transition metal phosphides such as P nanosheets, CoP nanowires and NiCoP nanowires are used as working electrodes to perform CV cyclic treatment, the overpotential and Tafel slope of electro-catalytic hydrogen production of the material are both remarkably reduced, the electro-catalytic hydrogen production performance is greatly improved, and the electro-catalytic performance of the material is more excellent.
CN109967131A discloses a preparation method of electrocatalytic hydrogen production molybdenum disulfide @ PVP material, dissolving amine heptamolybdate, thiourea and different amounts of PVP in ultrapure water, performing ultrasonic treatment for 30min to completely dissolve and disperse a sample, reacting the obtained solution in a 50mL polytetrafluoroethylene reaction kettle at 180-220 ℃ for 24h, centrifuging and drying the product after the reaction is finished, and obtaining MoS2The material shape of the @ PVP hydrogen production electrocatalyst is in the shape of a marigold nanometer flower sphere, the size is 100 nm-120 nm, and simultaneously MoS2The @ PVP nano ball is a MoS with 4-6 layers2@ PVP nanometer sheet. The ball can expose a large number of edge active sites, improve the density of intrinsic active centers, and the PVP can improve the MoS2Is used for the electrical conductivity of (1). Such MoS2The preparation time of the @ PVP electro-catalysis hydrogen evolution catalyst is short, the synthesis process is simple, and the MoS is further improved2Electrocatalytic hydrogen production activity.
CN108993542A discloses a monolayer MoS doped with magnetic atoms2And its use, with MoO3Powder, S powder and Fe2O3Or Co2O3Powder is used as precursor, and is prepared by simple chemical vapor synthesis method on SiO2Synthesis of large-area magnetic atom doped single-layer MoS on Si2Single layer of MoS doped with magnetic atoms2When the catalyst is used as a catalyst for electrocatalytic decomposition of water, the excellent electrocatalytic hydrogen production performance is shown. In which Co atoms are doped with a single layer of MoS2The sample showed goodThe initial voltage of hydrogen production catalysis is 200mV, the Tafel slope is as low as 45mV/dec, and the hydrogen production catalysis performance is close to noble metal Pt with the advantage of electrocatalysis performance. By one-step vapor deposition method, compared to pure single-layer MoS2Through the doping of magnetic atoms, the catalytic performance of the material is greatly improved, and the material becomes an effective means for material modification.
CN109908922A discloses a transition metal chalcogenide homojunction and its preparation method and application. The preparation method comprises the steps of firstly taking Mo powder and S powder as precursors, and synthesizing MoS in a closed quartz tube through simple solid-phase reaction2Flakes and then MoO3With KSCN as a precursor for the reaction on MoS by a simple hydrothermal method2Synthesis of MoS on sheet2Nanosheet forming MoS2And (4) forming a homojunction. MoS synthesis by two-step synthesis2MoS synthesized by solid-phase reaction method successfully modified by nanosheet2Surface of the sheet, MoS2The edge states of the nanosheets are fully exposed when the MoS is such that2When the homojunction is used as a catalyst for electrocatalytic water decomposition, the catalyst shows excellent electrocatalytic hydrogen production performance, the initial potential is 210mV, the Tafel slope is as low as 47mV/dec, the same is close to a noble metal Pt catalyst, and compared with a pure MoS catalyst2For the nano-sheet, the catalytic performance is obviously improved.
CN105951123A discloses a preparation method of NiCoP nanowire electro-catalytic electrode, firstly, the surface of nickel is pretreated, the oxide layer on the surface of foam nickel is removed, mixing with a solution containing nickel ions and cobalt ions, placing the mixture in a high-pressure reaction kettle, growing a nickel-cobalt salt compound precursor through hydrothermal, washing and drying to obtain the precursor, then, carrying out the phosphorization process of the nickel-cobalt salt compound precursor, calcining the sodium dihydrogen hypophosphite powder and the nickel-cobalt salt/foamed nickel sheet at the high temperature of 300-500 ℃ for 3-5.5h under the protection of nitrogen, naturally cooling, the NiCoP nano-wire electro-catalytic electrode is obtained after washing and drying, the surface of the nano-wire is rough and uniformly grows on a 3D reticular foam nickel substrate, the specific surface area and the conductivity of the electro-catalytic material are effectively improved, and the electrode material is subjected to electro-catalytic hydrogen production performance test in 1M KOH electrolyte at 10 mA/cm.2The overpotential under the current density is 109mV, the Tafel slope is 88.5mV/dec, compared with the common electrocatalytic hydrogen evolution material, the electrocatalytic hydrogen evolution material has obviously superior electrocatalytic hydrogen production performance, and meanwhile, the reaction synthesis equipment is simple, and the reaction materials are rich.
CN107829106A discloses a preparation method of a molybdenum sulfide/carbon nitride composite material, and a product and application thereof. Dissolving a certain amount of 1-imidazole-4-formic acid in an acetonitrile solution to form a uniform ligand solution, dissolving ammonium thiomolybdate in dimethylformamide according to a certain proportion, adding the solution into the ligand solution, stirring to fully dissolve ammonium molybdate in the ligand solution, simultaneously adding cellulose as a substrate material, adding a certain amount of cyanamide for coating, performing hydrothermal reaction on the mixed solution in a polytetrafluoroethylene reaction kettle, washing and drying to obtain solid powder (a cyanamide coated molybdenum sulfide intermediate), calcining the intermediate in nitrogen protection for 4 hours, and finally naturally cooling to obtain the molybdenum sulfide/carbon nitride composite material with the 3D structure. Molybdenum sulfide with a 3D structure is dendritic, is mostly in a 5-7-layer structure and can be effectively combined with a carbon nitride material, electrons are promoted to rapidly migrate between interfaces due to the existence of a heterojunction structure between molybdenum sulfide and carbon nitride in the novel molybdenum sulfide/carbon nitride composite material, and the prepared composite material shows excellent electrocatalytic hydrogen production performance and can be used as an efficient electrode material for hydrogen production catalyzed by electrolyzed water.
CN107501088A discloses a preparation method and application of a copper-based metal organic framework material, wherein an organic ligand H is adopted under a sealing condition4Adding hydrochloric acid into a mixed solution of Ddpb and 2.5 crystal water copper nitrate in N, N-dimethylformamide and water, adjusting the pH to 3, performing ultrasonic treatment for 30 minutes, performing solvothermal reaction at the reaction temperature of 90 ℃, and reacting for 36 hours to obtain the metal organic framework material with a crystal structure, namely the 1, 3-bis (3 ', 5' -dicarboxyphenyl) benzene Cu-based metal organic framework material. The material is used as a working electrode for electrocatalytic performance test, and the initial potential of the material is 210-250 mV. The metal organic framework material obtained by the synthesis method has simple synthesis process, high crystallization purity, large porosity and the likeHas multiple advantages. Has good electrocatalytic hydrogen evolution performance.
Qin et al proposed polyoxometallate-based MOFs for electrocatalytic hydrogen production (HER), at 0.5M H2SO4Has an initial potential of 180mV and a current density of-10 mA cm-2When the overpotential is 237mV, the Tafel slope is 96mV/dec, the porosity of the MOF improves the catalytic activity of the electrocatalytic hydrogen production (HER).
Hod et al prepared a high porosity NU-1000 film as a support for depositing Ni-S electrocatalyst, showed significantly enhanced electrocatalytic hydrogen production (HER) performance in acidic medium (0.1M HCl), MOFs structure enabled proton transport to be faster, current density was-10 mA cm-2The overpotential is lower than 238 mV.
As described above, in the prior art, a variety of modification methods and various materials are disclosed to be applied to the research of improving the electrocatalytic hydrogen production performance, the electrocatalytic hydrogen evolution performance of transition metal sulfides, carbides, phosphides and nitrides and metal organic framework materials is improved to a certain extent, and part of the electrocatalytic hydrogen evolution performance is even close to the catalytic hydrogen evolution effect of noble metal Pt, so that the transition metal sulfides, carbides, phosphides and nitrides and metal organic framework materials become ideal materials capable of replacing noble metal Pt.
Therefore, based on the defects, how to design a simple, rapid, economic and environment-friendly method to prepare the novel molybdenum polysulfide/MOF composite material with controllable morphology and good performance is of great significance and is also a research hotspot and focus in the field of electrochemical energy at present, which is the foundation and the power of the completion of the invention.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the invention aims to provide a simple, quick, economic and environment-friendly method for preparing carbon cloth loaded MoS with controllable appearance and good performancexa/UiO-66 composite material,the transition metal sulfide is combined with the MOF material with stable chemical properties, and the electrocatalytic hydrogen evolution performance of the material is improved by combining the advantages of the transition metal sulfide and the MOF material.
As a first aspect of the invention, the invention provides a carbon cloth-supported MoSxThe preparation method of the/UiO-66 composite material adopts the technical scheme that the preparation method comprises the following steps:
s1: dissolving an inorganic metal zirconium ion-containing precursor, terephthalic acid and a sulfur-containing molybdenum source precursor into an organic solvent, carrying out ultrasonic treatment, and uniformly mixing to obtain a precursor reaction solution;
s2: cleaning the carbon cloth to remove surface impurities;
s3: transferring the precursor reaction solution into a reaction container, putting the carbon cloth treated in the step (2), carrying out closed reaction at high temperature and high pressure, after the reaction is finished, relieving the pressure to normal pressure, naturally cooling to room temperature, cleaning and drying to obtain the MoS loaded by the carbon clothxa/UiO-66 composite material.
MoS loaded on the carbon cloth of the present inventionxIn the method for preparing the/UiO-66 composite material, in step S1, the precursor containing the inorganic metal zirconium ions is zirconium chloride.
MoS loaded on the carbon cloth of the present inventionxIn the method for preparing the/UiO-66 composite material, in step S1, the sulfur-containing molybdenum source precursor is selected from the group consisting of ammonium tetrathiomolybdate, molybdenum dimethyldithiocarbamate, and ammonium polythiomolybdate ((NH)4)2Mo3S13·nH2O) or a mixture of any more thereof, most preferably ammonium tetrathiomolybdate.
MoS loaded on the carbon cloth of the present inventionxIn the preparation method of the/UiO-66 composite material, in step S1, the organic solvent is any one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP), and most preferably N, N-Dimethylformamide (DMF).
MoS loaded on the carbon cloth of the present inventionxIn the preparation method of the/UiO-66 composite material, in the step S1, the precursor containing inorganic metal zirconium ions and the sulfur-containing precursorThe mass ratio of the molybdenum source precursors is 1:0.2-2, and may be, for example, 1:0.2, 1:0.5, 1:1, or 1:2, and most preferably 1: 2.
MoS loaded on the carbon cloth of the present inventionxIn the preparation method of the/UiO-66 composite material, in step S1, the amount of the organic solvent is not particularly limited, and may be, for example, an amount that is easy to react and/or perform post-treatment, and in step S2, the acid used for carbon cloth treatment may be concentrated nitric acid or concentrated hydrochloric acid, and those skilled in the art can make appropriate selections and determinations, and thus detailed description is omitted.
MoS loaded on the carbon cloth of the present inventionxIn the preparation method of the/UiO-66 composite material, the step S3 is as follows:
s3-1: and (4) transferring the precursor reaction solution obtained in the step (S1) to a stainless steel high-pressure reaction kettle with a 50mL Teflon substrate, putting the carbon cloth cleaned in the step (S2), sealing, heating to 100-160 ℃ from room temperature, and keeping at the temperature for 20-30 hours.
S3-2: naturally cooling the reaction solution to room temperature, taking out the carbon cloth, washing the carbon cloth for a plurality of times by using absolute ethyl alcohol, and then drying the carbon cloth in vacuum to obtain the MoS loaded on the carbon clothxa/UiO-66 composite material.
In step S3-1, the precursor reaction solution obtained in step S1 is transferred to a 50mL Teflon-substrate stainless steel high-pressure reaction kettle, carbon cloth cleaned in step S2 is placed in the stainless steel high-pressure reaction kettle, and then the reaction kettle is sealed and heated from room temperature to 100-160 ℃ and kept at the temperature for 20-30 hours. Most preferably for 24 hours.
The inventors have found that when such a preparation method is employed, carbon cloth-supported MoS of a specific morphology and excellent electrocatalytic hydrogen evolution performance can be obtainedxThe composite material is/UiO-66, and when some process parameters such as the raw material dosage ratio are changed, the photocatalytic composite material with good performance can not be obtained.
In a second aspect, the present invention relates to a carbon cloth-supported MoS obtained by the above-mentioned preparation methodxa/UiO-66 composite material.
The inventors found that the carbon cloth supported MoSx/UiThe O-66 composite material has excellent electro-catalysis performance, and the electro-catalysis hydrogen production (HER) electrode prepared from the O-66 composite material has excellent electrochemical performance, such as high catalytic activity, good stability, long service life and the like, so that the O-66 composite material can be applied to the technical field of hydrogen production by water electrolysis, and has good application prospect and industrialization potential.
Thus, in a third aspect, the invention relates to said carbon cloth supported MoSxUse of a/UiO-66 composite material in electrocatalytic hydrogen production.
In a fourth aspect, the invention also relates to an evaluation method of the electrocatalytic hydrogen production, which specifically comprises the following steps:
MoS loaded with the carbon clothxthe/UiO-66 composite material is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the carbon rod is used as an auxiliary electrode, and the anode is arranged in an acid medium (0.5M H)2SO4) In the method, cyclic voltammetry (LSV, CV) tests are carried out in a certain voltage range by utilizing an electrochemical workstation, and electrochemical impedance and i-t stability tests are carried out. And calculating the overpotential of the catalytic hydrogen evolution of the material and the Tafel slope according to the detection result so as to evaluate the electrocatalytic hydrogen evolution activity of the material.
Wherein, in the research of electrocatalytic hydrogen production, the MoS loaded by the carbon clothxIn the cyclic voltammetry LSV testing process of the/UiO-66 composite material, the testing voltage range is-0.4V-0V.
The inventor finds that the carbon cloth loaded MoS with specific morphology obtained by the inventionxthe/UiO-66 composite material effectively improves proton transfer by combining transition metal sulfide with metal organic framework material, has lower initial potential and Tafel slope, shows excellent catalytic performance, provides a brand-new and efficient catalytic material for hydrogen production by water electrolysis, becomes a favorable material for replacing noble metal Pt, and has great application potential and industrial value in the industrial field.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 shows a carbon cloth-supported MoS prepared in example 1 of the present inventionxLow power Scanning Electron Micrographs (SEM) of the/UiO-66 composite;
FIG. 2 shows a carbon cloth-supported MoS prepared in example 1 of the present inventionxTransmission Electron Micrographs (TEM) and high resolution transmission electron micrographs of the/UiO-66 composite (i.e., FIGS. 2(e) and 2 (f));
FIG. 3 shows a carbon cloth-supported MoS prepared in example 1 of the present inventionxX-ray diffraction pattern (XRD) of the/UiO-66 composite;
FIG. 4 shows a carbon cloth-supported MoS prepared in example 1 of the present inventionxX-ray photoelectron spectroscopy (XPS) of the/UiO-66 composite;
FIG. 5 shows a carbon cloth-supported MoS prepared in example 1 of the present inventionxNitrogen adsorption desorption isotherms (BET) of the/UiO-66 composite;
FIG. 6 shows a carbon cloth-supported MoS prepared in example 1 of the present inventionxThermogravimetric plot (TGA) of the/UiO-66 composite;
FIG. 7 shows a carbon cloth-supported MoS prepared in example 1 of the present inventionxLSV curves (FIG. 7a), Tafel plots (FIG. 7b), electrochemical impedance plots (FIG. 7c) and i-t stability plots (FIG. 7d) for the/UiO-66 composite;
FIG. 8 shows a carbon cloth-supported MoS prepared in example 1 of the present inventionxCyclic voltammogram CV curves of the/UiO-66 composite and comparison.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
S1: adding zirconium chloride and ammonium tetrathiomolybdate with the mass ratio of 5:10 into a proper amount of organic solvent N, N-dimethylformamide, adding terephthalic acid as an organic ligand, carrying out ultrasonic treatment for 30 minutes, and uniformly mixing to obtain a precursor reaction solution;
s2: treating the carbon cloth with organic solvents of acetone, ethanol, deionized water and concentrated nitric acid to remove surface impurities;
s3: transferring the precursor reaction solution into a reaction container, putting the carbon cloth into the reaction container, carrying out closed reaction at high temperature and high pressure, after the reaction is finished, relieving the pressure to normal pressure, naturally cooling to room temperature, cleaning and drying to obtain the MoS loaded by the carbon clothxa/UiO-66 composite material. The method specifically comprises the following steps:
s3-1: the precursor reaction solution obtained in step S1 was transferred to a 50mL teflon-substrate stainless steel autoclave, and the carbon cloth cleaned in step S2 was placed therein, and then heated from room temperature to 120 ℃ in a sealed state, and left at that temperature for 24 hours.
S3-2: naturally cooling the reaction solution to room temperature, taking out the carbon cloth, washing the carbon cloth for a plurality of times by using absolute ethyl alcohol, and then drying the carbon cloth in vacuum to obtain the MoS loaded on the carbon clothxa/UiO-66 composite material. It was named C1.
Examples 2 to 4: examination of raw material dosage ratio
Examples 2-4 were carried out by performing the same procedure as in example 1 except that in step S1, zirconium chloride and ammonium tetrathiomolybdate were used in the different material amount ratios shown in Table 1 below, and the raw material amount ratios and composite material names used are shown in Table 1 below.
TABLE 1 composite materials prepared with different raw material ratios
Examples 5 to 8: investigation of different kinds of materials
Examples 5 to 6: examples 5 to 6 were carried out in the same manner as in example 1 except that the materials shown in the following Table 2 were used in step S1.
Examples 7 to 8: examples 7 to 8 were carried out in the same manner as in example 1 except that the materials shown in Table 2 below were used in step S1.
See in particular table 2 below.
TABLE 2 composite materials made with different material compositions
Microscopic characterization
MoS loaded on the carbon cloth obtained in example 1xthe/UiO-66 composite material is subjected to microscopic characterization by a plurality of different means, and the results are as follows:
1. as can be seen from the low power Scanning Electron Micrograph (SEM) of FIG. 1, the carbon cloth-supported MoSxthe/UiO-66 composite material has uniform appearance, and MoS is anchored on the UiO-66/carbon cloth materialxThen, it can be observed that the nano-small particles are uniformly dispersed on the carbon fiber, and the UiO-66 size is obviously reduced, and the particle size is about 50 nm.
2. MoS on carbon cloth is further demonstrated as seen by Transmission Electron Microscopy (TEM) of FIG. 2xThe nanoparticle characteristic of UiO-66, no lattice fringes of UiO-66 are observed in high resolution transmission electron microscopy FIG. 2(a, b, c), since the material is prone to damage under high energy electron beam irradiation.
FIG. 2(e) and FIG. 2(f) are the MoS in FIG. 2(d), respectivelyxHigh resolution transmission electron microscopy images of/UiO-66/carbon cloth. No MoS observed2The lattice fringes of (2), which indicate MoSxIs amorphous, and UiO-66 and MoS are observed in FIG. 2(c) and FIG. 2(f)xThe pores on the surface of the/UiO-66 nano particles prove the metal organic framework structure and the porous characteristic of the UiO-66 nano particles and the MoSxThe possibility of anchoring therein.
3. As can be seen from the X-ray diffraction pattern (XRD) of FIG. 3, MoS was produced in the XRD diffraction pattern of the sample obtained with zirconium chloride and ammonium tetrathiomolybdate as the thiomolybdate sourcexthe/UiO-66/carbon cloth composite material only shows carbon peaks, and FIG. 3(b) shows a single synthetic MoSxIs also amorphous, and the MoS in the material is shown by the comparison and the results of the transmission electron micrographxIs amorphous. There are also some characteristic peaks of UiO-66 in the material.
4. X-ray photoelectron spectroscopy (XPS) from FIG. 4) It can be seen that both peaks at 228.2 and 226.7eV correspond to MoSxMoS in/UiO-66/CC compositesxThe two new peaks at S2S, 229.4 and 232.2eV of (g) are MoS2Binding energy of nanoparticles, Mo at 236.0eV is mainly MoO3Fig. 4(b) further confirms the S-rich molybdenum sulfide structure by high resolution XPS of Sp.
5. As can be seen from the nitrogen adsorption/desorption isotherms of FIG. 5, FIGS. 5(a) (b) are desorption curves of UiO-66, and the specific surface area of UiO-66 is 961m2g-1Pore volume of 0.438cm3g-1The average pore size was 0.49 nm. FIG. 5(c) (d) addition of (NH)4)2MoS4Thereafter, C1 (MoS) prepared as in example 1xUiO-66/carbon cloth) presents mixed type I and IV adsorption and desorption isotherms, and the surface area is 19m2g-1Pore volume of 0.031cm3g-1The average pore size was 0.84 nm.
Therefore, the occupation of the MOFs cage and the MoS are well demonstrated by comparing these specific surface area and pore size distribution dataxModification of the channel surface of UiO-66 by nanoparticles, which means MoSxSuccessfully incorporated into UiO-66.
6. As can be seen by thermogravimetric analysis (TGA) of FIG. 6, by UiO-66 and MoSxThermogravimetric analysis of/UiO-66, evaluation of Zr and Mo/Zr content thermogravimetric data show two major weight loss stages. For the UiO-66, the weight loss in the first stage (. about.150 ℃ C.) was 7.44%, due to H2Release of O and DMF molecules, and MoSxThe weight loss of/UiO-66 was 7.87%, which was attributable to H2Liberation of O and DMF molecules, and MoS in airxIs partially oxidized. During the second stage (. about.800 ℃ C.), for UiO-66 and MoSxfor/UiO-66, weight losses of 54.44% and 45.95% were attributed to decomposition of organic ligands in the framework and MoSxTotal oxidation of (1). The remaining 38.12% and 46.18% by weight should correspond to ZrO respectively2And ZrO2/MoO3Percentage of (c).
Preparation method of electrocatalytic hydrogen evolution electrode C1 electrode
Mixing all the materialsCarbon cloth-loaded MoS obtained in example 1xthe/UiO-66 composite material C1 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a carbon rod is used as an auxiliary electrode, and the working electrode is placed in an acid medium (0.5M H)2SO4) In the method, cyclic voltammetry (LSV, CV) tests are carried out in a certain voltage range by utilizing an electrochemical workstation, and electrochemical impedance and i-t stability tests are carried out.
Preparation method of electrocatalytic hydrogen evolution electrode C2-C6
The preparation method is repeated by respectively replacing the composite material C1 in the preparation method of the electrocatalytic hydrogen evolution electrode C1 with C2-C6, and other operations are not changed, so that the electrocatalytic hydrogen evolution electrodes using C2-C6 are sequentially obtained and named as C2, C3, C4, C5 and C6 electrodes.
Preparation method of electrocatalytic hydrogen evolution electrode C7-C8
A. Grinding and polishing a glassy carbon electrode in alumina water slurry with the particle size of 0.35 mu m, then sequentially ultrasonically washing the glassy carbon electrode in proper amount of acetone, absolute ethyl alcohol and high-purity water for 30 seconds, and drying the glassy carbon electrode by using nitrogen to obtain a pretreated glassy carbon electrode;
B. dispersing the materials C7 and C8 obtained in the examples 7 to 8 in an ethanol water solution with the mass percentage concentration of 50%, and then performing ultrasonic dispersion for 10 minutes to obtain a uniformly mixed solution; dripping the uniformly mixed solution onto the pretreated glassy carbon electrode, uniformly covering the pretreated glassy carbon electrode with the uniformly mixed solution, and drying at room temperature; and dropwise adding a nafion ethanol solution with the mass percent concentration of 5.5% on the glassy carbon electrode again, and drying at room temperature to obtain the electro-catalytic hydrogen evolution electrode, which is named as C7 and C8 electrodes.
7. FIG. 7 shows the carbon cloth-supported MoS prepared in examples 1 and 2 of the present inventionxThe material with different molybdenum content ratios is 0.5M H2SO4Electrochemical tests were performed to evaluate the catalytic efficiency of the electrocatalyst using the Tafel slope. FIG. 7(b) is a Tafel slope for various samples, where the Tafel slope of C1 is about 46mV/dec, and other composites of various ratios also exhibit smaller Tafel slopes.
FIG. 7(c) MoS at different molybdenum content ratiosxComparison of Electrochemical Impedance (EIS) of/UiO-66/carbon cloth composite. They were carried out at an applied potential of 200mV (vs AgCl/Ag). The C1 impedance was minimal, indicating that its electrocatalytic hydrogen production (HER) charge transfer was faster than the other samples. As the content of the molybdenum is increased, the charge transfer rate of the synthesized composite material is increased.
FIG. 7(d) MoS study by potentiostatic techniquexThe stability of the/UiO-66/carbon cloth composite, showing the change in current density with time at a fixed overpotential, the sample C1 of example 1 remained stable for six hours of stability testing, demonstrating the good stability of the material.
Thus demonstrating the carbon cloth loaded MoS of the present inventionxthe/UiO-66 composite material has excellent electro-catalysis hydrogen evolution performance and can be applied to the technical field of hydrogen production by water electrolysis.
8. MoS from FIG. 8xFrom the results of the electrochemical active area test of the/UiO-66/carbon cloth composite, the number of active sites is evaluated from the electrochemical active surface area (ECSA), C1 has a larger active area, and the electrochemical active area is increased due to the existence of a large amount of molybdenum sulfide active sites.
The electrocatalytic performance of C2-C4 was tested according to the same electrochemical method as described above, and the electrocatalytic performance data for C1 of example 1 are shown in the table below for comparison.
TABLE 3 comparison of the Properties of the composites obtained at different ratios of raw materials
Therefore, the overpotential and Tafel slope of C2-C4 are small, but the electrocatalytic hydrogen production performance is weaker than that of C1. The result shows that the molybdenum content has obvious influence on the electrocatalytic hydrogen production performance of the composite material, and the excellent electrocatalytic Hydrogen Evolution (HER) performance is shown by effectively reducing the charge transfer impedance and increasing the active surface area and the number of active sites.
From the above, it can be seen from all the examples that the preparation of the inventionThe method obtains the carbon cloth loaded MoS with unique morphology and structure through the synergistic combination and coordination of specific process steps, process parameters and the likexthe/UiO-66 composite material has good electrocatalytic hydrogen production performance, and is an ideal catalytic material capable of replacing noble metal Pt.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. MoS loaded by carbon clothxThe preparation method of the/UiO-66 composite material is characterized by comprising the following steps:
s1: dissolving an inorganic metal zirconium ion-containing precursor, terephthalic acid and a sulfur-containing molybdenum source precursor into an organic solvent, carrying out ultrasonic treatment, and uniformly mixing to obtain a precursor reaction solution;
s2: cleaning the carbon cloth to remove surface impurities;
s3: transferring the precursor reaction solution into a reaction container, putting the carbon cloth treated in the step (2), carrying out closed reaction at high temperature and high pressure, after the reaction is finished, relieving the pressure to normal pressure, naturally cooling to room temperature, cleaning and drying to obtain the MoS loaded by the carbon clothxa/UiO-66 composite material.
2. Carbon cloth loaded MoS according to claim 1xThe preparation method of the/UiO-66 composite material is characterized by comprising the following steps: the precursor containing inorganic metal zirconium ions is zirconium chloride.
3. A carbon cloth loaded MoS according to claim 1xThe preparation method of the/UiO-66 composite material is characterized by comprising the following steps: the sulfur-containing molybdenum source precursor is selected from any one or a mixture of any more of ammonium tetrathiomolybdate, molybdenum dimethyldithiocarbamate and ammonium polythiomolybdate.
4. Carbon cloth loaded MoS according to claim 1xThe preparation method of the/UiO-66 composite material is characterized by comprising the following steps: in step S1, the organic solvent is any one of N, N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone.
5. Carbon cloth loaded MoS according to claim 1xThe preparation method of the/UiO-66 composite material is characterized in that in the step S3: the temperature of the sealing reaction is set to be 100-160 ℃ from room temperature, and the sealing reaction is kept for 20-30 hours at the temperature; then naturally cooling the reaction solution to room temperature, taking out the carbon cloth, washing the carbon cloth with absolute ethyl alcohol for a plurality of times, and then drying the carbon cloth in vacuum to obtain the MoS loaded on the carbon clothxa/UiO-66 composite material.
6. Carbon cloth loaded MoS according to claim 1xThe preparation method of the/UiO-66 composite material is characterized by comprising the following steps: in step S1, the mass ratio of the inorganic metal zirconium ion-containing precursor to the sulfur-containing molybdenum source precursor is 1: 0.2-2.
7. A carbon cloth-supported MoS prepared by the method of any one of claims 1 to 6xa/UiO-66 composite material.
8. The carbon cloth-supported MoS of claim 7xThe application of the/UiO-66 composite material as a catalyst in electrocatalytic hydrogen production.
9. The carbon cloth-supported MoS of claim 7xThe method for evaluating the electrocatalytic hydrogen production performance of the/UiO-66 composite material is characterized by comprising the following steps of:
MoS loaded with the carbon clothxThe method comprises the steps of taking a/UiO-66 composite material as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a carbon rod as an auxiliary electrode, performing cyclic voltammetry test or linear sweep voltammetry test in an acidic medium by utilizing an electrochemical workstation within a certain voltage range, and performingAnd (4) testing electrochemical impedance and i-t stability, and calculating the overpotential and tafel slope of the material for hydrogen generation by catalysis according to the detection result so as to evaluate the electrocatalytic hydrogen evolution activity of the material.
10. The evaluation method according to claim 9, characterized in that: the carbon cloth-loaded MoSxIn the linear sweep voltammetry test process of the/UiO-66 composite material, the test voltage range is-0.4V-0V.
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111495394A (en) * | 2020-05-21 | 2020-08-07 | 南京师范大学 | Carbon cloth loaded CoS2/MoS2Heterojunction composite material and preparation method and application thereof |
CN111871463A (en) * | 2020-07-14 | 2020-11-03 | 南昌航空大学 | Preparation method of electrocatalytic full-decomposition water material based on ZIF-67 and UiO-66 double MOFs |
CN112927769A (en) * | 2021-01-26 | 2021-06-08 | 华南理工大学 | MOFs material defect structure prediction method based on pore size distribution curve |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170158502A1 (en) * | 2012-03-14 | 2017-06-08 | Board Of Regents, The University Of Texas System | Photochemical Processes and Compositions for Methane Reforming Using Transition Metal Chalcogenide Photocatalysts |
CN108118362A (en) * | 2018-01-09 | 2018-06-05 | 国家纳米科学中心 | A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application |
CN109046424A (en) * | 2018-08-09 | 2018-12-21 | 武汉科技大学 | A kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof |
-
2019
- 2019-09-10 CN CN201910853460.1A patent/CN110694693A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170158502A1 (en) * | 2012-03-14 | 2017-06-08 | Board Of Regents, The University Of Texas System | Photochemical Processes and Compositions for Methane Reforming Using Transition Metal Chalcogenide Photocatalysts |
CN108118362A (en) * | 2018-01-09 | 2018-06-05 | 国家纳米科学中心 | A kind of molybdenum disulfide electro-catalysis production hydrogen electrode and its preparation method and application |
CN109046424A (en) * | 2018-08-09 | 2018-12-21 | 武汉科技大学 | A kind of UiO-66-NH of highly effective hydrogen yield2/TiO2/Ti3C2Composite photo-catalyst and preparation method thereof |
Non-Patent Citations (5)
Title |
---|
DAI XIAOPING ET AL.: ""Molybdenum Polysulfide Anchored on Porous Zr-Metal Organic Framework To Enhance the Performance of Hydrogen Evolution Reaction"", 《JOURNAL OF PHYSICAL CHEMISTRY C》 * |
HAO XUQIANG ET AL.: ""Peculiar synergetic effect of MoS2 quantum dots and graphene on Metal-Organic Frameworks for photocatalytic hydrogen evolution"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
YANGUANG LI ET AL.: ""MoS2 Nanoparticles Grown on Graphene: An Advanced Catalyst for the Hydrogen Evolution Reaction"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
刘宏芳 著: "《交叉学科研究生高水平课程系列教材 纳米材料化学与器件(第1版)》", 31 July 2019, 华中科技大学出版社 * |
黄克靖 著: "《二维过渡金属二硫属化合物的电化学储能应用(第1版)》", 30 September 2018, 冶金工业出版社 * |
Cited By (12)
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CN114345374B (en) * | 2020-09-27 | 2024-03-08 | 武汉理工大学 | Preparation method of amorphous molybdenum polysulfide hydrogen evolution electrocatalyst constructed on carbon cloth |
CN112927769A (en) * | 2021-01-26 | 2021-06-08 | 华南理工大学 | MOFs material defect structure prediction method based on pore size distribution curve |
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