CN108686710B - Two-dimensional metal-organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution material and preparation method thereof - Google Patents
Two-dimensional metal-organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution material and preparation method thereof Download PDFInfo
- Publication number
- CN108686710B CN108686710B CN201810461343.6A CN201810461343A CN108686710B CN 108686710 B CN108686710 B CN 108686710B CN 201810461343 A CN201810461343 A CN 201810461343A CN 108686710 B CN108686710 B CN 108686710B
- Authority
- CN
- China
- Prior art keywords
- molybdenum disulfide
- organic framework
- dimensional metal
- hydrogen evolution
- nanocomposite
- 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.)
- Active
Links
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 57
- 239000001257 hydrogen Substances 0.000 title claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 48
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims abstract description 51
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 84
- 239000006185 dispersion Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000004729 solvothermal method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- -1 4-carboxy-phenyl Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 9
- 235000019441 ethanol Nutrition 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 14
- 229910052961 molybdenite Inorganic materials 0.000 description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002803 fossil fuel Substances 0.000 description 4
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明提供一种二维金属有机框架/二硫化钼纳米复合电催化析氢材料，所述材料包括互相分散的二维金属有机框架纳米片M‑TCPP和二硫化钼纳米片MoS2，其中，所述M选自Co2+、Ni2+中的至少一种，所述TCPP为5,10,15,20‑四(4‑羧基‑苯基)‑卟啉，所述M与Mo离子的摩尔比为1：0.4～8，本发明还提供了一种所述材料的制备方法；所述制备方法能够使材料表面的析氢反应活性位点增多，MoS2的导电性增强，显著提高所述二维金属有机框架/二硫化钼纳米复合电催化析氢材料的电催化析氢性能，为开发低价格、高效率的电催化析氢催化剂提供一种新的方法。
The present invention provides a two-dimensional metal-organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution material. The material comprises two-dimensional metal-organic framework nanosheets M-TCPP and molybdenum disulfide nanosheets MoS 2 dispersed with each other, wherein the Described M is selected from at least one in Co 2+ , Ni 2+ , described TCPP is 5,10,15,20-tetrakis (4-carboxy-phenyl)-porphyrin, the mole of described M and Mo ion The ratio is 1:0.4-8, the present invention also provides a preparation method of the material; the preparation method can increase the active sites for hydrogen evolution reaction on the surface of the material, enhance the conductivity of MoS 2 , and significantly improve the two The electrocatalytic hydrogen evolution performance of dimensional metal-organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution materials provides a new method for the development of low-cost and high-efficiency electrocatalytic hydrogen evolution catalysts.
Description
Technical Field
The invention relates to the technical field of electrocatalytic hydrogen evolution, in particular to a two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material and a preparation method thereof.
Background
Along with the increasing energy crisis and environmental pollution problemsAt the same time, people's normal life and production have been seriously threatened. However, fossil energy sources (coal, oil and natural gas) have been the main sources of energy in the world, they are limited reserves of non-renewable energy and combustion products can severely pollute the environment. With the increase of the demand of fossil fuels and the reduction of the reserves of fossil fuels, people are more urgent to develop green and efficient renewable energy sources. The hydrogen energy is called the cleanest energy of the twenty-first century, and has wide application prospect due to a series of advantages, such as rich sources, high combustion heat value, only water generation after the hydrogen is combusted, and the like. The most common hydrogen production methods at present are water electrolysis hydrogen production and fossil fuel hydrogen production. However, fossil fuel is a non-renewable energy source, and although the method can produce a large amount of hydrogen, the application prospect is worried. Water is abundant in the earth, and hydrogen is produced by electrolyzing water, so that the hydrogen is inexhaustible. At present, electric energy can be directly produced in various modes, and the cost is low. Therefore, the method for producing hydrogen by electrolyzing water can be applied to large-scale production, and has the advantages of high hydrogen production efficiency, simple process and operation process, no environmental pollution and the like. Electrolyzed water can be divided into two half-cell reactions, namely, Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). Both oxygen evolution reactions and hydrogen evolution reactions require the use of electrocatalysts to reduce the overpotential of the electrochemical reactions. Overpotential refers to the difference between the applied voltage and the thermodynamic reaction electromotive force in an electrochemical process. The greater the overpotential, the greater the applied voltage that needs to be applied, and the more power is consumed. It is therefore necessary to develop highly efficient hydrogen evolution catalysts which significantly reduce the hydrogen evolution overpotential. Currently, the platinum group noble metals are electrocatalysts with the highest hydrogen evolution efficiency, and can realize hydrogen evolution reaction at a voltage very close to the electromotive force of thermodynamic reaction. However, since precious metal resources are scarce and expensive, large-scale industrial production of hydrogen is impossible. Scientists have been working on developing a catalyst with abundant sources and high catalytic hydrogen evolution performance to replace the platinum group noble metal. Of these materials, two-dimensional (2D) Transition Metal Dichalcogenide (TMD) nanoplates have become an attractive HThe ER electrocatalyst type has good electrocatalytic hydrogen evolution performance. Molybdenum disulfide (MoS) as a typical layered TMD material2) Nanoplatelets have recently been widely used as HER catalysts, which show several thin S-Mo-S layers by weak van der waals interactions. Both theoretical and experimental studies show that MoS2Δ G ofH*Does approach thermal neutrality, resulting in MoS2May be an effective HER catalyst, which is of great interest because of its abundant resources and low cost. But the conductivity of the catalyst is poor, and the exposed hydrogen evolution reaction active sites are relatively few, so that the electrocatalytic hydrogen evolution performance of the catalyst is still to be greatly improved.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material and a preparation method thereof, wherein the material has high electrocatalytic hydrogen evolution performance.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalysis hydrogen evolution material comprises two-dimensional metal organic framework nanosheets M-TCPP and molybdenum disulfide nanosheets MoS which are mutually dispersed2Wherein M is selected from Co2+、Ni2+Is 5,10,15, 20-tetrakis (4-carboxy-phenyl) -porphyrin, the molar ratio of M to Mo ions being 1: 0.4 to 8.
A preparation method of the two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material comprises the following steps:
(1) synthesizing a two-dimensional metal organic framework nanosheet M-TCPP, wherein M is selected from Co2+、Ni2+TCPP is 5,10,15, 20-tetrakis (4-carboxy-phenyl) -porphyrin; dispersing the two-dimensional metal organic framework nanosheet in a dispersing agent to prepare a dispersion liquid A;
(2) synthesis of molybdenum disulfide nanosheet MoS2Dispersing the molybdenum disulfide nanosheets in a dispersing agent to prepare a dispersion liquid B;
(3) and dropwise adding the dispersion liquid A into the dispersion liquid B, carrying out ultrasonic treatment, stirring, separating and drying to obtain the two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material.
Preferably, the two-dimensional metal organic framework nanosheet is synthesized by a solvothermal method; the molybdenum disulfide nanosheet is synthesized by a hydrothermal method.
Preferably, the solvothermal method is to drop an organic ligand solution into a metal ion solution, perform solvothermal reaction at 80 ℃, and obtain the two-dimensional metal organic framework nanosheet through separation and purification.
Preferably, the hydrothermal method is to perform hydrothermal reaction at 180 ℃ by taking soluble molybdate as a molybdenum source and L-cysteine as a sulfur source, and obtain the molybdenum disulfide nanosheet through separation and purification.
Preferably, the dispersant is ethanol.
Preferably, the ultrasonic treatment time in the step (3) is 25 minutes, and the stirring time is 12 hours.
The invention has the beneficial effects that: the preparation method provided by the invention is to introduce two-dimensional Metal Organic Framework (MOF) nanosheets into MoS2Preparing a two-dimensional metal organic framework/molybdenum disulfide nano composite electro-catalytic hydrogen evolution material two-dimensional MOF/MoS from nano sheets2The ultra-thin thickness, large specific surface area and fast electron transmission performance of the two-dimensional MOF are utilized to increase hydrogen evolution reaction active sites and specific surface area on the surface of the material, so that the electrocatalytic hydrogen evolution performance of the material is improved, and meanwhile, transition metal ions Co2+Or Ni2+Can enhance MoS2Conductivity of (2), regulation of MoS2The electro-catalysis hydrogen evolution performance of the structure is improved, and the two-dimensional MOF nano-sheet and the MoS are used2The electrocatalytic hydrogen evolution performance of the two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material can be obviously improved due to the synergistic interaction of the nano sheets, and a new method is provided for developing an electrocatalytic hydrogen evolution catalyst with low price and high efficiency.
Drawings
FIG. 1. the two-dimensional Co-MOF/MoS2-3 and two-dimensional Co-MOF nanosheet and MoS2Comparison graph of electrocatalytic hydrogen evolution performance of the nanosheets.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, BPY is 4,4 '-bipyridine, PVP is polyvinylpyrrolidone, DMF is N, N' -dimethylformamide and TCPP is 5,10,15, 20-tetrakis (4-carboxy-phenyl) -porphyrin.
Example 1
The preparation method of the two-dimensional metal organic framework/molybdenum disulfide nano composite electrocatalytic hydrogen evolution material comprises the following steps:
(1) 4.4mg of Co (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP are added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, magnetic stirring is carried out until the solution is completely dissolved to obtain a solution (1), 4mg TCPP is weighed and added to a mixture of 1.5ml DMF and 0.5ml absolute ethanol, ultrasonic treatment is carried out for 15 minutes until the solution is completely dissolved to obtain a solution (2), then the solution (2) is dropwise added to the solution (1), after ultrasonic treatment for 25 minutes, the solution is transferred to a 18ml Teflon-lined reactor, the temperature of an oven is adjusted to 80 ℃, and the oven is placed in the oven to react for 24 hours. Naturally cooling to room temperature, performing centrifugal separation to obtain red precipitate, washing with ethanol twice to obtain two-dimensional Co-MOF nanosheets, and dispersing the two-dimensional Co-MOF nanosheets into 0.5ml of ethanol to form a dispersion liquid A;
(2) 0.4g of Na2MoO40.65g L cysteine and 60mL deionized water, then sealed in a 100mL Teflon-lined reactor and heated at 180 ℃ for 18 hours, after the reaction cooled naturally to room temperature, the black precipitate was collected by centrifugation, washed 2 times with deionized water and ethanol, and dried under vacuum at 80 ℃ for 12 hours to obtain MoS2Nanosheets prepared by mixing 10mg of the MoS2Nano meterDispersing the tablets into 20ml of ethanol to obtain a dispersion liquid B;
(3) dropwise adding the dispersion liquid A into the dispersion liquid B, carrying out ultrasonic treatment for 20 minutes, finally stirring at room temperature for 12 hours, carrying out centrifugal separation to collect the obtained precipitate, washing with ethanol for a plurality of times, and then carrying out vacuum drying at 80 ℃ for 10 hours to obtain the nano composite Co-MOF/MoS2-3。
Example 2
The same procedure as in example 1 was used to prepare a nanocomposite Co-MOF/MoS2-1, except that in step (2) 1mg of said MoS is added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 3
The same procedure as in example 1 was used to prepare a nanocomposite Co-MOF/MoS2-2, except that in step (2) 5mg of said MoS is added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 4
The same procedure as in example 1 was used to prepare a nanocomposite Co-MOF/MoS2-4, except that in step (2) 20mg of said MoS is added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 5
The same procedure as in example 1 was used to prepare a nanocomposite Ni-MOF/MoS2-1 except that in step (1) 4.4mg of Ni (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, and in step (2) 1mg of the MoS was added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 6
The same procedure as in example 1 was used to prepare a nanocomposite Ni-MOF/MoS2-2 except that in step (1) 4.4mg of Ni (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 5mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 7
The same procedure as in example 1 was used to prepare a nanocomposite Ni-MOF/MoS2-3, except that in step (1) 4.4mg of Ni (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol.
Example 8
The same procedure as in example 1 was used to prepare a nanocomposite Ni-MOF/MoS24, except that in step (1) 4.4mg of Ni (NO)3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 20mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 9
Nanocomposite Co was prepared using the same procedure as in example 10.25Ni0.75-MOF/MoS2-1 except that in step (1) 1.1mg of Co (NO)3)2·6H2O、3.3mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, and in step (2) 1mg of the MoS was added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 10
Nanocomposite Co was prepared using the same procedure as in example 10.25Ni0.75-MOF/MoS2-2 except that in step (1) 1.1mg Co (NO)3)2·6H2O、3.3mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 5mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 11
Nanocomposite Co was prepared using the same procedure as in example 10.25Ni0.75-MOF/MoS2-3, except that in step (1) 1.1mg of Co (NO)3)2·6H2O、3.3mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP 4.5ml DMF and 15ml of absolute ethyl alcohol mixture.
Example 12
Nanocomposite Co was prepared using the same procedure as in example 10.25Ni0.75-MOF/MoS2-4, except that in step (1) 1.1mg Co (NO)3)2·6H2O、3.3mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 20mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 13
Nanocomposite Co was prepared using the same procedure as in example 10.5Ni0.5-MOF/MoS2-1 except that in step (1) 2.2mg of Co (NO)3)2·6H2O、2.2mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, and in step (2) 1mg of the MoS was added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 14
Nanocomposite Co was prepared using the same procedure as in example 10.5Ni0.5-MOF/MoS2-2 except that in step (1) 2.2mg of Co (NO)3)2·6H2O、2.2mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 5mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 15
Nanocomposite Co was prepared using the same procedure as in example 10.5Ni0.5-MOF/MoS2-3 except that in step (1) 2.2mg of Co (NO)3)2·6H2O、2.2mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol.
Example 16
The same procedure as in example 1 was followedPreparation of nanocomposite Co0.5Ni0.5-MOF/MoS2-4, except that in step (1) 2.2mg of Co (NO)3)2·6H2O、2.2mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 20mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 17
Nanocomposite Co was prepared using the same procedure as in example 10.75Ni0.25-MOF/MoS2-1 except that in step (1) 3.3mg Co (NO)3)2·6H2O、1.1mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, and in step (2) 1mg of the MoS was added2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 18
Nanocomposite Co was prepared using the same procedure as in example 10.75Ni0.25-MOF/MoS2-2 except that in step (1) 3.3mg Co (NO)3)2·6H2O、1.1mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 5mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Example 19
Nanocomposite Co was prepared using the same procedure as in example 10.75Ni0.25-MOF/MoS2-3, except that in step (1) 3.3mg Co (NO)3)2·6H2O、1.1mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol.
Example 20
Nanocomposite Co was prepared using the same procedure as in example 10.75Ni0.25-MOF/MoS2-4, except that in step (1) 3.3mg Co (NO)3)2·6H2O、1.1mg Ni(NO3)2·6H2O, 1.6mg BPY, 10mg PVP were added to a mixture of 4.5ml DMF and 1.5ml absolute ethanol, 20mg of the MoS in step (2)2The nanosheets were dispersed in 20ml of ethanol to give a dispersion B.
Test example
The electrocatalytic hydrogen evolution performance of the material prepared in example 1 was tested using the Shanghai Chenghua CHI660E electrochemical workstation, and all potential values were converted to relatively Reversible Hydrogen Electrode (RHE) voltages by adding (0.2415+0.059pH) V. The test was carried out using a three-electrode system, a glassy carbon electrode (diameter 3mm, area 0.070785 cm)2) The working electrode, the counter electrode and the reference electrode are respectively a platinum wire and silver-silver chloride (3M KCl), and the electrolyte is 0.5mol/L sulfuric acid solution. The relevant settings of the linear scan test parameters are as follows: the scanning range is from 0.1 to 0.6V (vs. RHE), the linear scanning speed is 5mV/s, and the sampling interval is 1 mV.
The working electrode was prepared as follows: first, 0.05 μm Al was used for a glassy carbon electrode on a chamois2O3Polishing the polishing powder for 15min, cleaning with absolute ethyl alcohol in an ultrasonic machine for 2min, then ultrasonically cleaning in distilled water for two times, each for 2min, obtaining a bright mirror surface, and then drying for later use. Weighing 4mg of dried Co-MOF/MoS2-3 samples 16 μ L of 5 wt% Nafion and 1mL of dispersion were added, and 5 μ L of the catalyst dispersion drop was pipetted onto the surface of the polished glassy carbon electrode and allowed to air dry at room temperature for future use.
FIG. 1 shows Co-MOF/MoS under the same conditions2-3、MoS2The electrocatalytic hydrogen evolution performance of the nano-sheet and the two-dimensional Co-MOF nano-sheet shows that Co-MOF/MoS2-3 nanocomposite material exhibiting a MoS ratio2The nano-sheet and the two-dimensional Co-MOF nano-sheet have better electro-catalytic hydrogen evolution activity. Mixing MoS2After being combined with a two-dimensional Co-MOF nano sheet, the composite nano material has high activity on HER. The lowest initial potential for starting hydrogen evolution is about 170mV, above which the cathodic current rises rapidly to 10mA + cm at 262mV-2。
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810461343.6A CN108686710B (en) | 2018-05-15 | 2018-05-15 | Two-dimensional metal-organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810461343.6A CN108686710B (en) | 2018-05-15 | 2018-05-15 | Two-dimensional metal-organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108686710A CN108686710A (en) | 2018-10-23 |
| CN108686710B true CN108686710B (en) | 2021-02-23 |
Family
ID=63847365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810461343.6A Active CN108686710B (en) | 2018-05-15 | 2018-05-15 | Two-dimensional metal-organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108686710B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109701666A (en) * | 2018-11-26 | 2019-05-03 | 西北师范大学 | A porphyrin-based optoelectronic material reinforced by molybdenum disulfide nanosheets |
| CN110116025A (en) * | 2019-05-30 | 2019-08-13 | 河北科技大学 | Covalent triazine class framework compound and MoS2The preparation method of compound liberation of hydrogen catalyst and the application of liberation of hydrogen catalyst |
| CN111036307B (en) * | 2019-10-18 | 2022-09-27 | 南京理工大学 | A kind of preparation method of composite high-efficiency oxygen evolution catalyst |
| CN111167521B (en) * | 2020-01-18 | 2023-02-17 | 河南师范大学 | Catalytic material, preparation method thereof, photocatalyst and electrocatalyst |
| CN111995760A (en) * | 2020-07-17 | 2020-11-27 | 扬州大学 | Cobalt-metal organic framework nanosheet and preparation method and application thereof |
| CN112206821B (en) * | 2020-10-12 | 2022-05-13 | 中国科学技术大学 | A kind of transition metal nitrogen-containing macrocyclic compound catalyst for electrolysis of water to produce oxygen and its preparation method and application |
| KR102474942B1 (en) * | 2020-11-16 | 2022-12-06 | 고려대학교 산학협력단 | Composite for hydrogen-generating catalyst having metal-organic framework and method of preparing the same |
| CN112853373B (en) | 2021-01-08 | 2021-12-03 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Intergrown twin crystal Ni2Mo6S6O2/MoS2Synthesis method of two-dimensional nanosheet |
| CN113130216B (en) * | 2021-03-31 | 2022-11-15 | 上海应用技术大学 | A kind of molybdenum disulfide@ZIF-67@CoO-NF composite material and its synthesis and application |
| CN113101366B (en) * | 2021-04-08 | 2023-08-25 | 东南大学 | A molybdenum disulfide-based material with both photothermal and photodynamic properties and its preparation method |
| CN113403631B (en) * | 2021-07-06 | 2022-07-26 | 常州大学 | Granular CuCo-MOF/MoS2 catalyst and its preparation method and application |
| CN114540874A (en) * | 2021-12-02 | 2022-05-27 | 西南大学 | A preparation method of Er-MOF/MoS2 and its electrocatalytic application |
| CN114808027B (en) * | 2022-04-27 | 2024-07-02 | 哈尔滨理工大学 | N-MoS with high-efficiency electrocatalytic hydrogen evolution performance2/COF-C4N composite catalyst and preparation method thereof |
| CN114832834B (en) * | 2022-05-20 | 2023-11-14 | 常州大学 | L-CNSx/MCS composite photocatalyst and preparation method and application thereof |
| CN115094438B (en) * | 2022-07-05 | 2023-09-29 | 安徽师范大学 | A one-dimensional structure molybdenum diselenide/molybdenum-MOF composite nanomaterial and its preparation method and application |
| CN118988409B (en) * | 2024-08-30 | 2025-03-18 | 萱柯氢能科技(广东)有限公司 | Preparation method and application of composite photocatalyst for visible light catalytic hydrogen evolution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5709936A (en) * | 1995-03-23 | 1998-01-20 | Lockheed Martin Energy Systems, Inc. | Composite coating for low friction and wear applications and method thereof |
| WO2015171791A1 (en) * | 2014-05-06 | 2015-11-12 | Massachusetts Institute Of Technology | Compositions and methods comprising conductive metal organic frameworks and uses thereof |
| CN105344309A (en) * | 2015-12-01 | 2016-02-24 | 宁波诺丁汉新材料研究院有限公司 | Mercury removal agent with nano laminated structure |
| CN107195935A (en) * | 2012-05-21 | 2017-09-22 | 辉光能源公司 | CIHT dynamical systems |
-
2018
- 2018-05-15 CN CN201810461343.6A patent/CN108686710B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5709936A (en) * | 1995-03-23 | 1998-01-20 | Lockheed Martin Energy Systems, Inc. | Composite coating for low friction and wear applications and method thereof |
| CN107195935A (en) * | 2012-05-21 | 2017-09-22 | 辉光能源公司 | CIHT dynamical systems |
| WO2015171791A1 (en) * | 2014-05-06 | 2015-11-12 | Massachusetts Institute Of Technology | Compositions and methods comprising conductive metal organic frameworks and uses thereof |
| CN105344309A (en) * | 2015-12-01 | 2016-02-24 | 宁波诺丁汉新材料研究院有限公司 | Mercury removal agent with nano laminated structure |
Non-Patent Citations (2)
| Title |
|---|
| Nanocomposites of 2D-MoS2 nanosheets with the metal–organic framework, ZIF-8;K. Pramoda，et al;《Dalton Trans.》;20160801;第45卷(第35期);第13810-13816页 * |
| 金属有机框架模板法制备二硫化钼复合材料及光催化分解水产氢研究;马冰;《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》;20171115(第11期);第B014-130页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108686710A (en) | 2018-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108686710B (en) | Two-dimensional metal-organic framework/molybdenum disulfide nanocomposite electrocatalytic hydrogen evolution material and preparation method thereof | |
| CN109046408B (en) | A kind of composite hydrogen evolution electrocatalytic material and preparation method and application thereof | |
| CN108374179B (en) | A kind of preparation method and application of the compound nitrogen-doped carbon material of two cobaltous selenide of Fe2O3 doping | |
| CN109065897B (en) | Phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst and preparation method and application thereof | |
| CN108325565A (en) | Multi-functional carbon-based base metal elctro-catalyst of one kind and its preparation method and application | |
| CN111001428B (en) | A kind of metal-free carbon-based electrocatalyst and preparation method and application | |
| CN104577141A (en) | Sulfur doped graphene modified electrode as well as preparation method and application of sulfur doped graphene modified electrode | |
| CN113019398B (en) | High-activity self-supporting OER electrocatalyst material and preparation method and application thereof | |
| CN111408385A (en) | A kind of preparation method of Fe5Ni4S8 hydrogen evolution electrocatalytic material | |
| CN108358181A (en) | Hydrogen evolution reaction electrocatalyst of phosphide, preparation method and application | |
| CN110215928A (en) | A kind of preparation method of sulfur doping phosphatization Ni nanopowders and its application in electrolysis water | |
| CN113235104A (en) | ZIF-67-based lanthanum-doped cobalt oxide catalyst and preparation method and application thereof | |
| CN106992304A (en) | It is a kind of to nitrogenize the Preparation method and use that carbon-based composite oxygen reduction electro-catalyst modifies disk electrode | |
| CN106654304A (en) | CuO/rGO composite material having efficient electrocatalysis oxygen reducing performance | |
| CN110611105A (en) | The preparation method of ORR catalyst | |
| CN111450851A (en) | A kind of preparation method of sulfur-doped cobalt-based nanometer oxygen evolution electrocatalyst | |
| CN106268876A (en) | The preparation of selenizing stainless steel foam electrolysis water catalysis material and application | |
| Shojaeifar et al. | MnO2–NiO–MWCNTs nanocomposite as a catalyst for methanol and ethanol electrooxidation | |
| CN108585044A (en) | The simple preparation and electro-catalysis application of a kind of Co-MoO2 nanospheres with mylikes structures | |
| CN115805317A (en) | A kind of ruthenium iridium alloy material and its preparation method and application | |
| CN107570154B (en) | Iron-based hydrogen production electrocatalyst and preparation method thereof | |
| CN110479239A (en) | One kind is with a thickness of 1.5nm bismuth nano-wire and its preparation method and application | |
| CN113584504A (en) | Ru/RuO2/MoO2Composite material and preparation method and application thereof | |
| CN114044502B (en) | Monoclinic phase zinc pyrophosphate, preparation method and application thereof | |
| CN108677211B (en) | Carbon nano-tube/poly closes ionic liquid/copper complex complex light anode catalyst system and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20241126 Address after: Room 12303, Unit 1, Building 6, Huayuan Hailan City Phase II, Xuanwu East Road, Chanba Ecological Zone, Xi'an City, Shaanxi Province 710000 Patentee after: Shaanxi Shanmu Construction Engineering Co.,Ltd. Country or region after: China Address before: No.1 Xijing Road, Chang'an District, Xi'an City, Shaanxi Province 710100 Patentee before: XIJING University Country or region before: China |
|
| TR01 | Transfer of patent right |