CN114540874A - Er-MOF/MoS2Preparation method and electrocatalytic application thereof - Google Patents
Er-MOF/MoS2Preparation method and electrocatalytic application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 23
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000012621 metal-organic framework Substances 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000013110 organic ligand Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000000840 electrochemical analysis Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000013384 organic framework Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a simple and green two-step hydrothermal method for preparing Er-MOF/MoS2And the application thereof in the field of hydrogen production by electrolyzing water. As for the traditional electrocatalyst, the noble metal catalyst has good hydrogen evolution catalytic activity, but the commercial application of the noble metal catalyst is greatly limited by the defects of high value, less storage and the like of the noble metal catalyst, and the product (Er-MOF/MoS) of the invention2) Has good electrocatalytic hydrogen evolution performance. The rare earth metal-based organic framework material is innovatively used in the field of electrocatalytic materials, the composite structure with uniform appearance and structure is obtained by a two-step hydrothermal process, the optimal catalytic effect can be achieved, the catalytic activity is high, and Er-MOF/MoS is obtained in the hydrogen evolution reaction2Overpotential ratio of (MoS)2Over-potential of (j =10 mA/cm)2Potential of time) is shifted positive by 146 mV.
Description
Technical Field
The invention relates to the technical field of hydrogen evolution catalyst production, in particular to Er-MOF/MoS2The preparation method and the application thereof.
Background
Development of clean renewable energy due to energy and environmental crisis caused by overuse of fossil fuelsThe source is in need of promoting sustainable development. The hydrogen energy has high energy density, and the combustion has no carbon emission, thereby being one of the most ideal substitutes of fossil fuels. The hydrogen production by water electrolysis is an important method for producing hydrogen, however, additional energy is inevitably consumed in the water electrolysis process to overcome the overpotential due to the overpotential. Noble metals (such as Pt) remain the most excellent electrocatalysts available, but their high cost and scarcity severely hamper their use in industry. Due to the unique two-dimensional structure and abundant catalytic sites, the molybdenum disulfide has great application potential in the field of electrocatalysis and is widely applied and researched. Rare earth-based metal organic frameworks (RE-MOFs), as an important subclass of MOFs, are rarely used in the field of electrocatalysis, in part because of their inherent poor catalytic capabilities. Growth of MoS on Er-MOF by using Er-MOF as a carrier2Thus Er-MOF and MoS2Synergistic effect of increased Er-MOF/MoS2Hydrogen evolution reactivity of the catalyst.
Disclosure of Invention
Based on the problems, the invention provides Er-MOF/MoS2The preparation method and the application of the composite material are characterized in that Er-MOF/MoS with uniform and stable morphology and structure is obtained by a two-step hydrothermal method2And the optimal catalytic effect can be achieved.
In order to achieve the above purpose, the technical scheme of the invention is realized by the following technical scheme:
Er-MOF/MoS2A preparation method of the composite material, namely Er-MOF/MoS2The preparation method of the composite material comprises the following steps:
(1) preparing raw materials: dissolving 1mmol of metal source erbium nitrate and 1mmol of organic ligand oxalic acid in 15mL of deionized water to form a solution A, adding 1mmol of organic ligand trimesic acid into 15mL of N, N-Dimethylformamide (DMF) to form a solution B for later use, and then mixing and stirring the solution A and the solution B uniformly to form a solution C to obtain a mixed solution for later use;
(2) centrifugal drying: placing the mixed solution in a high-temperature polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 12h, centrifuging, taking a precipitate, washing the precipitate with water and alcohol for several times, and drying in a drying oven in vacuum to obtain a sample as a precursor Er-MOF;
(3) secondary water heating: dissolving 0.25mmol of molybdenum source and 1mmol of sulfur source in a mixed solution of 15mL of deionized water; 50-150mg of precursor Er-MOF is uniformly dispersed in the solution;
(4) adjusting the pH value: adjusting the pH value of the mixed solution to 3, and transferring the mixed solution to a reaction kettle to obtain a precursor solution for reaction for later use;
(5) centrifugal drying: placing the mixed solution in a high-temperature polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 24h, centrifuging, taking precipitate, washing the precipitate with water and alcohol for a plurality of times, and drying in a drying oven in vacuum to obtain uniform and stable Er-MOF/MoS2；
(6) Hydrogen evolution electrochemical tests were performed.
Preferably, the metal organic framework in step (1) is prepared by using two organic ligand sources, namely oxalic acid and trimesic acid.
Preferably, 50-150mg Er-MOF and MoS are adopted in the step (3)2The components are compounded according to the proportion.
Preferably, erbium nitrate and trimesic acid are dissolved in deionized water and then are stirred for 30min respectively in the step (1), and then are subjected to ultrasonic treatment for 10-60min under the conditions that the power is 60-80W and the ultrasonic frequency is 20-40Hz, and then are stirred for 10-30min at the stirring speed of 200-500 rad/min.
Preferably, the reagent for adjusting pH in the step (4) is glacial acetic acid (C)2H4O2）。
Preferably, the rotation speed of the centrifugation in the step (2) is 4000-.
Preferably, the pressure of vacuum drying in the oven in the step (2) is 0.08-0.10MPa, the temperature is 60 ℃, and the drying time is 12-24 h.
The invention has the beneficial effects that: the Er-MOF with regular appearance and uniform distribution is prepared by a hydrothermal method and two organic ligands; Er-MOF/MoS with uniform and stable morphology and structure is prepared by using hydrothermal method2(ii) a Er-MOF/MoS prepared by the invention2The hydrogen evolution catalyst has good crystallinity and purityDegree, Er-MOF/MoS of the invention2The catalyst is a novel electrocatalyst with high catalytic performance and high stability, and further helps to solve the energy crisis and dilemma faced by the human society at present.
Drawings
For purposes of clarity and clarity of the objects and advantages of the invention, the following detailed description of the invention is provided in conjunction with the accompanying drawings, in which:
FIG. 1 shows example 1 (Er-MOF/MoS)2) And example 4 (MoS)2) XRD patterns of the prepared catalyst and precursor Er-MOF;
FIG. 2 is a graph of the Hydrogen Evolution (HER) linear scan for various catalysts of examples 1-4;
FIG. 3 shows the results of example 1 (Er-MOF/MoS)2) And example 4 (MoS)2) SEM images of the prepared catalyst and precursor Er-MOF;
FIG. 4 is a graph of the hydrogen evolution stability of the catalyst of example 1.
FIG. 1 shows example 1 (Er-MOF/MoS)2) And example 4 (MoS)2) XRD patterns of the prepared catalyst and precursor Er-MOF; the diffraction peaks of the samples are not obvious, which shows that the crystallinity of the synthesized samples is not high and is in an indefinite form, namely Er-MOF/MoS2A26 ℃ carbon peak was detected, indicating successful MoS2Growing onto Er-MOF.
FIG. 2 is a plot of the Hydrogen Evolution (HER) linear scan for various catalysts of examples 1-4; the graph shows that the product properties are different due to different Er-MOF amounts; the proportioning performance of 100mg Er-MOF is optimal; h at 0.5M2SO4In the electrolyte, a carbon rod was used as a counter electrode, an Ag/AgC1 electrode was used as a reference electrode, and HER polarization curve studies were carried out on various catalysts of examples 1 to 4 at a scanning speed of 5 mV. s-1(ii) a As can be seen from the figure, Er-MOF has poor hydrogen evolution catalytic activity, and MoS grows on the Er-MOF2Synthesis of Er-MOF/MoS2In the case of catalyst, Er-MOF/MoS2Shows remarkably improved hydrogen evolution catalytic activity, Er-MOF/MoS2Specific MoS in hydrogen evolution reaction2Overpotential of nanotubes (j =10 mA/cm)2Potential of the same) positive shift 146mV, which demonstrates Er-MOF/MoS2BiMoS2Has more excellent hydrogen evolution reaction activity.
FIG. 3 shows example 1 (Er-MOF/MoS)2) And example 4 (MoS)2) SEM images of the prepared catalyst and precursor Er-MOF; the synthesized Er-MOF is uniformly distributed as can be seen from the figure; MoS2The material does not have agglomeration phenomenon, Er-MOF/MoS2The substance is provided with a plurality of holes; this shows that Er-MOF/MoS can be successfully synthesized by a two-step hydrothermal method2。
FIG. 4 shows example 1 (Er-MOF/MoS)2) Preparing a hydrogen evolution stability diagram of the catalyst; from the figure, Er-MOF/MoS can be seen2Has good hydrogen evolution activity, and the current is basically stable after the i-t test for 12 hours, which indicates that the Er-MOF/MoS is2The hydrogen evolution catalyst has good stability.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments, but 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.
Example 1:
Er-MOF/MoS2Method for preparing said Er-MOF/MoS2The preparation method comprises the following steps:
(1) preparing raw materials: dissolving 1mmol of metal source erbium nitrate and 1mmol of organic ligand oxalic acid in 15mL of deionized water to form a solution A, adding 1mmol of organic ligand trimesic acid into 15mL of N, N-Dimethylformamide (DMF) to form a solution B for later use, and then mixing and stirring the solution A and the solution B uniformly to form a solution C to obtain a mixed solution for later use;
(2) centrifugal drying: placing the mixed solution in a high-temperature polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 12h, centrifuging, taking a precipitate, washing the precipitate with water and alcohol for several times, and drying in a drying oven in vacuum to obtain a sample as a precursor Er-MOF;
(3) secondary water heating: dissolving 0.25mmol of sodium molybdate and 1mmol of thioacetamide in a mixed solution of 15mL of deionized water; 50-150mg of precursor Er-MOF is uniformly dispersed in the solution;
(4) adjusting the pH value: adjusting the pH value of the mixed solution to 3, and transferring the mixed solution to a reaction kettle to obtain a precursor solution for reaction for later use;
(5) centrifugal drying: placing the mixed solution in a high-temperature polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 24h, centrifuging, taking precipitate, washing the precipitate with water and alcohol for a plurality of times, and drying in a drying oven in vacuum to obtain uniform and stable Er-MOF/MoS2；
(6) Hydrogen evolution electrochemical tests were performed.
Example 2:
similar to the step 1, the difference is that the secondary hydrothermal treatment in the step (3) uses 50mg of precursor Er-MOF to be uniformly dispersed in the solution and is named Er-MOF/MoS2-50、Er-MOF/MoS2-150。
Example 3:
similar to the step 1, the difference is that the secondary hydrothermal reaction in the step (3) uses 150mg of precursor Er-MOF to be uniformly dispersed in the solution.
Example 4:
similar to the step 1, the difference is that the first step Er-MOF preparation is not carried out, namely no precursor Er-MOF is added, and MoS is directly carried out2The synthesis of (2).
Example 5:
electrocatalytic test electrochemical measurements were carried out in a standard three-electrode electrochemical test using an electrochemical workstation (CHI760E, CHInstores) using carbon rods and Ag/AgC1 electrodes (0.5M Na as electrolyte) respectively2SO4) As a counter electrode and a reference electrode, a glassy carbon electrode (GCE, diameter 3mm) was used as a working electrode.
1) The electrocatalytic material prepared in examples 1 to 5 was dispersed in 1mL of ethanol at a matching concentration of 5mg to obtain an electrode modification solution, and the electrode modification solution was coated on a working electrode with a loading of 0.21 mg-cm-2After dryingCoating the electrode protection solution again, and drying again;
2) electrochemical measurements were carried out using an electrochemical workstation (CHI760E, CHInstores) using carbon rods and Ag/AgC1 electrodes (electrolyte 0.5M H)2SO4) As a counter electrode and a reference electrode, the working electrode is a glassy carbon electrode (GCE, diameter of 3 mm);
3) the data obtained in step (2) are generated into fig. 2 and fig. 4.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
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 (8)
1. Simple and green hydrothermal method for preparing Er-MOF/MoS2Method, characterized in that said Er-MOF/MoS2The preparation method comprises the following steps:
(1) preparing raw materials: dissolving 1mmol of metal source erbium nitrate and 1mmol of organic ligand oxalic acid in 15mL of deionized water to form a solution A, adding 1mmol of organic ligand trimesic acid into 15mL of N, N-Dimethylformamide (DMF) to form a solution B for later use, and then mixing and stirring the solution A and the solution B uniformly to form a solution C to obtain a mixed solution for later use;
(2) centrifugal drying: placing the mixed solution in a high-temperature polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 12h, centrifuging, taking a precipitate, washing the precipitate with water and alcohol for several times, and drying in a drying oven in vacuum to obtain a sample as a precursor Er-MOF;
(3) secondary water heating: dissolving 0.25mmol of sodium molybdate and 1mmol of thioacetamide in a mixed solution of 15mL of deionized water, and uniformly dispersing 50-150mg of precursor Er-MOF in the solution;
(4) adjusting the pH value: adjusting the pH value of the mixed solution to 3, and transferring the mixed solution to a reaction kettle to obtain a precursor solution for reaction for later use;
(5) centrifugal drying: placing the mixed solution in a high-temperature polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 24 hours, centrifuging, taking precipitate, washing the precipitate with water and alcohol for several times, and drying in a drying oven in vacuum to obtain uniform and stable Er-MOF/MoS2；
(6) Hydrogen evolution electrochemical tests were performed.
2. An Er-MOF/MoS according to claim 12The preparation method is characterized by comprising the following steps: the preparation of the metal organic framework in the step (1) uses two organic ligand sources of oxalic acid and trimesic acid.
3. An Er-MOF/MoS according to claim 12The preparation method is characterized by comprising the following steps: 50-150mgEr-MOF and MoS adopted in the step (3)2And (4) compounding.
4. An Er-MOF/MoS according to claim 12The preparation method is characterized by comprising the following steps: in the step (1), erbium nitrate and trimesic acid are dissolved in deionized water and then are respectively stirred for 30min, and after mixing, the power is 60-80W, and the ultrasonic frequency is carried outUltrasonic treatment is carried out for 10-60min under the condition of the rate of 20-40Hz, and then stirring is carried out for 10-30min at the stirring speed of 200-500 rad/min.
5. The Er-MOF/MoS of claim 12The preparation method is characterized by comprising the following steps: the reagent for adjusting the pH value in the step (4) is glacial acetic acid (C)2H4O2）。
6. An Er-MOF/MoS according to claim 12The preparation method is characterized by comprising the following steps: the rotating speed of the centrifugation in the step (2) is 4000-.
7. An Er-MOF/MoS according to claim 12The preparation method is characterized by comprising the following steps: and (3) in the step (2), the vacuum drying pressure in the oven is 0.08-0.10MPa, the temperature is 60 ℃, and the drying time is 12 h.
8. An electrochemical analysis system comprising an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and an electrolyte, wherein the surface of the working electrode is coated with the Er-MOF/MoS of claim 12Preparing materials; in a standard three-electrode electrochemical test, HER measurements were performed using an electrochemical workstation (CHI760E, chinstraugents), using a carbon rod and an Ag/AgC1 electrode (electrolyte 0.5M H), respectively2SO4) As a counter electrode and a reference electrode, a glassy carbon electrode (GCE, diameter 3mm) was used as a working electrode.
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