CN116375088A - Cu-Mo-S nanowire and preparation method thereof - Google Patents
Cu-Mo-S nanowire and preparation method thereof Download PDFInfo
- Publication number
- CN116375088A CN116375088A CN202310625613.3A CN202310625613A CN116375088A CN 116375088 A CN116375088 A CN 116375088A CN 202310625613 A CN202310625613 A CN 202310625613A CN 116375088 A CN116375088 A CN 116375088A
- Authority
- CN
- China
- Prior art keywords
- mixed solution
- time threshold
- threshold
- nanowire
- substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002070 nanowire Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 46
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000011259 mixed solution Substances 0.000 claims abstract description 72
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000243 solution Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 57
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 57
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 57
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 57
- 239000008367 deionised water Substances 0.000 claims abstract description 49
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 49
- 239000002244 precipitate Substances 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 74
- 238000000034 method Methods 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 36
- 239000010949 copper Substances 0.000 description 21
- 230000009286 beneficial effect Effects 0.000 description 19
- 238000005245 sintering Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000007769 metal material Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 229910017267 Mo 6 S 8 Inorganic materials 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910021432 inorganic complex Inorganic materials 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
Abstract
The invention provides a Cu-Mo-S nanowire and a preparation method thereof, wherein the preparation method of the Cu-Mo-S nanowire comprises the following steps: dissolving copper nitrate, ammonium molybdate and trithiocyanic acid in deionized water, ultrasonically stirring for a first time threshold, and then adding an aniline solution to form a first mixed solution; the acid-base value of the first mixed solution is regulated dropwise through dilute hydrochloric acid until the first mixed solution is acidic, so that a second mixed solution is formed; standing the second mixed solution at the first temperature threshold for a second time threshold to obtain a precipitate; washing the precipitate for multiple times through ethanol and deionized water, and drying the precipitate at a second temperature threshold for a third time threshold; grinding the dried precipitate to obtain powder; and heating the powder to a third temperature threshold at a constant speed at a first speed threshold under the nitrogen atmosphere, and maintaining a fourth time threshold to obtain the Cu-Mo-S nanowire.
Description
Technical Field
The invention relates to the technical field of preparation of nanowires, in particular to a preparation method of a Cu-Mo-S nanowire and the Cu-Mo-S nanowire.
Background
The hydrogen energy has the characteristics of no pollution, renewable property and the like, and is honored as an optimal energy carrier in the 21 st century. Electrolytic water hydrogen production is an important way to obtain green hydrogen, and a noble metal catalyst with high price and low yield is one of main bottlenecks of commercialization, so that development of a catalytic material which is low in cost and can be compared with noble metals is a problem to be solved at present.
Disclosure of Invention
In order to solve or improve at least one of the above technical problems, an object of the present invention is to provide a method for preparing Cu-Mo-S nanowires.
It is another object of the present invention to provide a Cu-Mo-S nanowire.
To achieve the above object, a first aspect of the present invention provides a method for preparing Cu-Mo-S nanowires, comprising: dissolving copper nitrate, ammonium molybdate and trithiocyanic acid in deionized water, ultrasonically stirring for a first time threshold, and then adding an aniline solution to form a first mixed solution; the acid-base value of the first mixed solution is regulated dropwise through dilute hydrochloric acid until the first mixed solution is acidic, so that a second mixed solution is formed; standing the second mixed solution at the first temperature threshold for a second time threshold to obtain a precipitate; washing the precipitate for multiple times through ethanol and deionized water, and drying the precipitate at a second temperature threshold for a third time threshold; grinding the dried precipitate to obtain powder; and heating the powder to a third temperature threshold at a constant speed at a first speed threshold under the nitrogen atmosphere, and maintaining a fourth time threshold to obtain the Cu-Mo-S nanowire.
According to the technical scheme of the preparation method of the Cu-Mo-S nanowire provided by the invention, mo is doped by Cu 2 C-MoS 2 Changing the electronic structure of the outer layer of Mo, and changing the MoS of semiconductor property 2 The Cu-Mo-S compound which is converted into the Shefler phase with metallic property is beneficial to greatly improving the HER performance. In the technical scheme defined by the invention, the cheap transition metal material is used for replacing the noble metal material with high cost and limited yield, thereby being beneficial to reducing the production cost of the electrolyzed water. In addition, in the preparation process of the Cu-Mo-S nanowire, the electronic structure of the Mo outer layer is changed by Cu doped with Mo sulfide, so that the performance is improved, the catalytic activity is improved, and the electrolysis energy consumption is reduced.
Specifically, the preparation method of the Cu-Mo-S nanowire comprises the following steps:
firstly, copper nitrate, ammonium molybdate and trithiocyanic acid are dissolved in deionized water, and aniline solution is added after ultrasonic stirring for a first time threshold to form a first mixed solution. Copper nitrate is an inorganic chemical with the chemical formula Cu (NO) 3 ) 2 . Ammonium molybdate is an inorganic salt of the formula (NH 4 ) 2 MoO 4 . Trithiocyanate, i.e. cyanuric acid, with molecular formula C 3 H 3 N 3 S 3 . Deionized water refers to pure water from which impurities in ionic form have been removed. Copper nitrate, ammonium molybdate and trithiocyanic acid in a certain proportion are dissolved in deionized water. Alternatively, the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate is equal to the amount of the substance of trithiocyanic acid. Alternatively, the amount of the substance of copper nitrate is 5% to 70% of the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate. Alternatively, the amount of the substance of copper nitrate is equal to the amount of the substance of ammonium molybdate. Further, the solution is stirred by ultrasound for a first time threshold before the aniline solution is added. Ultrasonic stirring, i.e. ultrasonic stirring, using ultra-highThe solution is stirred by high shear forces generated by cavitation of acoustic waves. Aniline is also known as aminobenzene, which is an organic compound with a chemical formula of C 6 H 7 N is a colorless oily liquid. Dissolving aniline in organic solvent such as ethanol or diethyl ether to obtain aniline solution. Optionally, the volume ratio of deionized water to aniline solution is 50:1. alternatively, 0.05mmol (millimole) of copper nitrate, 0.95mmol of ammonium molybdate and 1mmol of trithiocyanic acid are dissolved in 50mL of deionized water, and after stirring ultrasonically for 30min, 1mL of aniline solution is added. Alternatively, 0.5mmol (millimole) of copper nitrate, 0.5mmol of ammonium molybdate and 1mmol of trithiocyanic acid are dissolved in 50mL of deionized water, and after stirring ultrasonically for 30min, 1mL of aniline solution is added. Alternatively, 0.5mmol (millimole) of copper nitrate, 0.5mmol of ammonium molybdate and 1mmol of trithiocyanic acid are dissolved in 50mL of deionized water, and after stirring ultrasonically for 30min, 1mL of aniline solution is added. The method comprises the steps of mixing copper nitrate, ammonium molybdate, trithiocyanic acid, deionized water and an aniline solution to obtain a first mixed solution;
and secondly, dropwise adjusting the acid-base value of the first mixed solution through dilute hydrochloric acid until the first mixed solution is acidic to form a second mixed solution. The pH value is pH value. Optionally, the pH of the first mixed solution is adjusted dropwise with dilute hydrochloric acid until the pH is 3.5. The aim of the step is to adjust the acid-base value of the first mixed solution to be an acidic condition and obtain a second mixed solution;
and thirdly, standing the second mixed solution at the first temperature threshold for a second time threshold to obtain a precipitate. The precipitate here is a Cu-Mo complex. And (3) placing the mixed solution in a baking oven at 50 ℃, and standing for 12 hours to obtain the Cu-Mo complex. The purpose of this step is to chemically react the chemical substances in the second mixed solution under acidic conditions and at a first temperature threshold to obtain a Cu-Mo complex. The first three steps are precursor preparation steps. The precursor is in a form of existence before the target product is obtained, and mostly exists in the form of organic and inorganic complexes or mixtures;
and fourthly, cleaning the precipitate for a plurality of times through ethanol and deionized water, and drying the precipitate for a third time threshold under a second temperature threshold. The purpose of the multiple cleaning and drying is to remove extraneous variables. Optionally, washing the precipitate with ethanol and deionized water for multiple times, and drying at 60deg.C for 4 hr;
and fifthly, grinding the dried precipitate to obtain powder. The powder obtained after grinding has larger contact area, which is beneficial to chemical reaction in the subsequent steps. Optionally, the ground powder is placed in a quartz boat. The quartz boat is also called quartz glass, and has the characteristic of high temperature resistance;
and step six, heating the powder to a third temperature threshold at a constant speed at a first speed threshold under the nitrogen atmosphere, and maintaining a fourth time threshold to obtain the Cu-Mo-S nanowire. Here nitrogen is used as shielding gas. Optionally, a quartz boat with powder placed therein is arranged in a tube furnace, the temperature is programmed to 800 ℃ at a temperature rising rate of 5 ℃/min under a nitrogen atmosphere, and the temperature is maintained for 5 hours, so that the Cu-Mo-S nanowire is obtained. Nanowires refer to one-dimensional structures that are confined below 100 nanometers in the lateral direction (without confinement in the longitudinal direction). Cu doping does not change Mo 2 C-MoS 2 Is a feature of (3). The Cu-Mo-S nanowire has a linear structure and a molecular formula of Cu 1.8 Mo 6 S 8 。
Molybdenum-based compounds have an outer electron structure similar to platinum and thus play an important role in the study of electrocatalyst Hydrogen Evolution Reactions (HER). MoS (MoS) 2 Is being studied extensively because it still shows stable and good HER activity in an acidic environment. MoS (MoS) 2 The main strategy of modification is to reduce the d track center position of Mo, weaken the Mo-H bond energy and improve the desorption capacity of hydrogen so as to improve the electrolysis efficiency. Electrocatalyst Hydrogen Evolution Reaction (HER) refers to the electrochemical generation of hydrogen using a catalyst.
The invention provides a preparation method of a Cu-Mo-S nanowire, which comprises the step of doping Mo with Cu 2 C-MoS 2 Changing the electronic structure of the outer layer of Mo, and changing the MoS of semiconductor property 2 The Cu-Mo-S compound which is converted into a Shevirel phase (Chevrel phase) with metallic property is beneficial to greatly improving the HER performance. In the technical proposal defined by the invention, inexpensive transition metal materials are used to replace expensive and outputThe limited noble metal material is beneficial to reducing the production cost of the electrolyzed water. In addition, in the preparation process of the Cu-Mo-S nanowire, the electronic structure of the Mo outer layer is changed by Cu doped with Mo sulfide, so that the performance is improved, the catalytic activity is improved, and the electrolysis energy consumption is reduced.
In addition, the technical scheme provided by the invention can also have the following additional technical characteristics:
in the above-described technical means, the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate is equal to the amount of the substance of trithiocyanic acid.
In the technical scheme, copper nitrate and ammonium molybdate are metal salts. The amount of the substance of the metal salt is equal to the amount of the substance of the trithiocyanic acid, i.e. the equimolar ratio of the metal salt to the trithiocyanic acid, to ensure that the Cu-Mo-S compound of the Sheffir phase can be prepared. The Cu-Mo-S compound is Cu-Mo-S nanowire.
In the above technical scheme, the amount of the substance of copper nitrate is 5% to 70% of the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate.
In this solution, it is ensured that the preparation of the Cu-Mo-S compound of the Sheffier phase is possible by controlling the percentage of copper nitrate in relation to the amount of substance of the metal salt.
In the above technical scheme, the amount of the substance of copper nitrate is equal to the amount of the substance of ammonium molybdate.
In this embodiment, the best performance of this mode of preparation is achieved by setting the copper nitrate and ammonium molybdate to equimolar amounts, at 0.5mol H 2 SO 4 The current density in the solution was 71.4mA/cm 2 . The current density is a vector unit and represents the current intensity and the flowing direction. The current density is equal to the electric quantity passing through a certain unit area in unit time; the direction of the current density is the normal vector of the corresponding section per unit area, and the direction is determined by the direction of positive charges through this section. Alternatively, the voltage is 400mV. Alternatively, the ratio of the amount of the substance of copper nitrate, the amount of the substance of ammonium molybdate, and the amount of the substance of trithiocyanic acid is 1:1:2.
in the above technical scheme, copper nitrate, ammonium molybdate and trithiocyanic acid are dissolved in deionized water, and after ultrasonic stirring for a first time threshold, aniline solution is added to form a first mixed solution, specifically: copper nitrate, ammonium molybdate and trithiocyanic acid are dissolved in deionized water, an aniline solution is added after ultrasonic stirring is carried out for a first time threshold, and the volume ratio of the deionized water to the aniline solution is 50:1, forming a first mixed solution.
In the technical scheme, the aim of the step is to mix copper nitrate, ammonium molybdate, trithiocyanic acid, deionized water and aniline solution to obtain a first mixed solution. The volume ratio of deionized water to aniline solution is controlled to ensure that the Cu-Mo-S compound of the Sheffier phase can be prepared.
In the above technical solution, the acid-base value of the first mixed solution is dropwise adjusted by dilute hydrochloric acid until the first mixed solution is acidic to form a second mixed solution, specifically: and (3) dropwise adjusting the pH value of the first mixed solution through dilute hydrochloric acid until the pH value is 3.5, so as to form a second mixed solution.
In this embodiment, the purpose of this step is to adjust the acid-base value of the first mixed solution to an acidic condition and obtain a second mixed solution. By quantitatively calibrating the acid-base value of the first mixed solution to 3.5, the reaction condition of the chemical substances can be ensured, and the Cu-Mo-S compound of the Sheffier phase can be prepared in the subsequent step.
In the above technical scheme, the precipitate is a Cu-Mo complex.
In this solution, the complex is also called a coordination compound, which is a compound having a characteristic chemical structure, and is formed by binding a central atom and a molecule or ion (called a ligand) surrounding it completely or partially through a coordination bond. The Cu-Mo complex is separated out in the form of a precipitate, so that the Cu-Mo complex is conveniently processed in the subsequent step to obtain the Cu-Mo-S compound of the Sheffier phase.
In the above technical solution, the first time threshold is 25min to 35min.
In the technical scheme, by controlling the ultrasonic stirring time, on one hand, the ultrasonic stirring time is prevented from being too short, and the copper nitrate, ammonium molybdate and trithiocyanic acid can be fully mixed in deionized water to carry out chemical reaction; on the other hand, the ultrasonic stirring is avoided for too long, which is beneficial to improving the preparation efficiency.
In the above technical solution, the first time threshold is 30min.
In the technical scheme, the time of ultrasonic stirring is controlled by setting the first time threshold to 30min, so that copper nitrate, ammonium molybdate and trithiocyanic acid can be fully mixed in deionized water for chemical reaction, and the preparation efficiency can be improved.
In the above technical solution, the second time threshold is 11h to 13h.
In the technical scheme, the standing time of the second mixed solution is controlled, so that on one hand, the excessively short standing time is avoided, and the yield of the required sediment is ensured; on the other hand, the long standing time is avoided, and the preparation efficiency is improved.
In the above technical solution, the second time threshold is 12h.
In the technical scheme, the second time threshold is set to be 12 hours, and the standing time of the second mixed solution is controlled, so that the yield of the required sediment can be ensured, and the preparation efficiency can be improved.
In the above technical solution, the third time threshold is 3h to 5h.
In the technical scheme, the drying time of the precipitate is controlled, so that on one hand, the too short drying time is avoided, extraneous factors are removed, and the preparation of the Cu-Mo-S compound of the Sheffier phase in the subsequent step is ensured; on the other hand, the method avoids overlong drying time and is beneficial to improving the preparation efficiency.
In the above technical solution, the third time threshold is 4h.
In the technical scheme, the third time threshold is set to be 4 hours, so that the drying time of the precipitate is controlled, irrelevant factors are removed, the preparation of the Sheffier-phase Cu-Mo-S compound in the subsequent step is ensured, and the preparation efficiency can be improved.
In the above technical solution, the fourth time threshold is 4h to 6h.
In the technical scheme, the high-temperature sintering time of the powder is controlled, so that on one hand, the high-temperature sintering time of the powder is prevented from being too short, and the Cu-Mo-S compound of the Sheffier phase is ensured to be prepared in the subsequent step; on the other hand, the method avoids overlong high-temperature sintering time of the powder, and is beneficial to improving the preparation efficiency.
In the above technical solution, the fourth time threshold is 5h.
In the technical scheme, the fourth time threshold is set to be 5 hours, and the high-temperature sintering time of the powder is controlled, so that the preparation of the Sheffier-phase Cu-Mo-S compound in the subsequent step can be ensured, and the preparation efficiency can be improved.
In the above technical solution, the first temperature threshold is 50 ℃; and/or the second temperature threshold is 60 ℃; and/or the third temperature threshold is 800 ℃.
In this technical scheme, the first temperature threshold is set to 50 ℃, and the environmental temperature of the second mixed solution when standing is controlled, so that the yield of the required precipitate can be ensured.
By setting the second temperature threshold to 60 ℃, the drying temperature of the precipitate is controlled, which is beneficial to removing extraneous factors, and ensuring that the Cu-Mo-S compound of the Sheffier phase is prepared in the subsequent step.
By setting the third temperature threshold to 800 ℃ and controlling the highest temperature of the powder at high temperature sintering, it is possible to ensure that the Cu-Mo-S compound of the Sheffier phase is produced in the subsequent step.
In the above technical solution, the first speed threshold is 4 ℃/min to 6 ℃/min.
In the technical scheme, the temperature rising rate of high-temperature sintering is controlled, so that on one hand, the excessively high temperature rising is avoided, and the temperature programming is realized; on the other hand, the temperature rise is avoided from being too slow, and the preparation efficiency is improved.
In the above technical solution, the first speed threshold is 5 ℃/min.
In the technical scheme, the Cu-Mo-S nanowire is formed by setting the first speed threshold to be 5 ℃/min, programming the temperature to 800 ℃ at the temperature rising rate of 5 ℃/min and sintering the powder at a high temperature after 5 hours.
The second aspect of the invention provides a Cu-Mo-S nanowire, which is manufactured by the preparation method of the Cu-Mo-S nanowire in any technical scheme.
According to the technical scheme of the Cu-Mo-S nanowire, the Cu-Mo-S nanowire is manufactured by the preparation method of the Cu-Mo-S nanowire in any technical scheme. In the technical scheme defined by the invention, the cheap transition metal material is used for replacing the noble metal material with high cost and limited yield, thereby being beneficial to reducing the production cost of the electrolyzed water. In addition, the Cu doped Mo sulfide changes the electronic structure of the Mo outer layer, so that the performance is improved, the catalytic activity is improved, and the electrolysis energy consumption is reduced.
Additional aspects and advantages of the present invention will be made apparent from the description which follows, or may be learned by practice of the invention.
Drawings
FIG. 1 shows a first flow chart of a method of fabricating Cu-Mo-S nanowires in accordance with one embodiment of the invention;
FIG. 2 shows a second flow chart of a method of fabricating Cu-Mo-S nanowires in accordance with one embodiment of the invention;
FIG. 3 shows an electron microscope image of a Cu-Mo-S nanowire under a 10um scale according to one embodiment of this invention;
FIG. 4 shows an electron microscope image of a Cu-Mo-S nanowire under a 1um scale according to one embodiment of this invention;
fig. 5 shows an X-ray diffraction pattern used to characterize the crystalline phase transition process.
Detailed Description
In order that the above-recited objects, features and advantages of embodiments of the present invention can be more clearly understood, a further detailed description of embodiments of the present invention will be rendered by reference to the appended drawings and detailed description thereof. It should be noted that, in the case of no conflict, the embodiments of the present application and the features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, however, embodiments of the invention may be practiced otherwise than as described herein, and therefore the scope of the present application is not limited to the specific embodiments disclosed below.
Cu-Mo-S nanowires and methods of preparing the same provided according to some embodiments of the present invention are described below with reference to fig. 1 to 4.
In one embodiment according to the present invention, as shown in fig. 1, the specific steps of the preparation method of Cu-Mo-S nanowire include:
s102, dissolving copper nitrate, ammonium molybdate and trithiocyanic acid in deionized water, and adding an aniline solution after ultrasonic stirring for a first time threshold to form a first mixed solution. Copper nitrate is an inorganic chemical with the chemical formula Cu (NO) 3 ) 2 . Ammonium molybdate is an inorganic salt of the formula (NH 4 ) 2 MoO 4 . Trithiocyanate, i.e. cyanuric acid, with molecular formula C 3 H 3 N 3 S 3 . Deionized water refers to pure water from which impurities in ionic form have been removed. Copper nitrate, ammonium molybdate and trithiocyanic acid in a certain proportion are dissolved in deionized water. Alternatively, the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate is equal to the amount of the substance of trithiocyanic acid. Alternatively, the amount of the substance of copper nitrate is 5% to 70% of the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate. Alternatively, the amount of the substance of copper nitrate is equal to the amount of the substance of ammonium molybdate. Further, the solution is stirred by ultrasound for a first time threshold before the aniline solution is added. Ultrasonic stirring is ultrasonic stirring, and the solution is stirred by using high shear force generated by cavitation of ultrasonic waves. Aniline is also known as aminobenzene, which is an organic compound with a chemical formula of C 6 H 7 N is a colorless oily liquid. Dissolving aniline in organic solvent such as ethanol or diethyl ether to obtain aniline solution. Optionally, the volume ratio of deionized water to aniline solution is 50:1. alternatively, 0.05mmol (millimole) of copper nitrate, 0.95mmol of ammonium molybdate and 1mmol of trithiocyanic acid are dissolved in 50mL of deionized water, and after stirring ultrasonically for 30min, 1mL of aniline solution is added. Alternatively, 0.5mmol (millimoles) Copper nitrate, 0.5mmol ammonium molybdate and 1mmol trithiocyanic acid were dissolved in 50mL deionized water and after stirring ultrasonically for 30min 1mL aniline solution was added. Alternatively, 0.5mmol (millimole) of copper nitrate, 0.5mmol of ammonium molybdate and 1mmol of trithiocyanic acid are dissolved in 50mL of deionized water, and after stirring ultrasonically for 30min, 1mL of aniline solution is added. The method comprises the steps of mixing copper nitrate, ammonium molybdate, trithiocyanic acid, deionized water and an aniline solution to obtain a first mixed solution;
s104, the acid-base value of the first mixed solution is adjusted dropwise through dilute hydrochloric acid until the first mixed solution is acidic, so that a second mixed solution is formed. The pH value is pH value. Optionally, the pH of the first mixed solution is adjusted dropwise with dilute hydrochloric acid until the pH is 3.5. The aim of the step is to adjust the acid-base value of the first mixed solution to be an acidic condition and obtain a second mixed solution;
and S106, standing the second mixed solution at the first temperature threshold for a second time threshold to obtain a precipitate. The precipitate here is a Cu-Mo complex. And (3) placing the mixed solution in a baking oven at 50 ℃, and standing for 12 hours to obtain the Cu-Mo complex. The purpose of this step is to chemically react the chemical substances in the second mixed solution under acidic conditions and at a first temperature threshold to obtain a Cu-Mo complex. The first three steps are precursor preparation steps. The precursor is in a form of existence before the target product is obtained, and mostly exists in the form of organic and inorganic complexes or mixtures;
and S108, cleaning the precipitate for a plurality of times through ethanol and deionized water, and drying the precipitate for a third time threshold at a second temperature threshold. The purpose of the multiple cleaning and drying is to remove extraneous variables. Optionally, washing the precipitate with ethanol and deionized water for multiple times, and drying at 60deg.C for 4 hr;
and S110, grinding the dried precipitate to obtain powder. The powder obtained after grinding has larger contact area, which is beneficial to chemical reaction in the subsequent steps. Optionally, the ground powder is placed in a quartz boat. The quartz boat is also called quartz glass, and has the characteristic of high temperature resistance;
s112, the powder is subjected to a first speed threshold under a nitrogen atmosphereAnd uniformly heating to the third temperature threshold value and maintaining the fourth time threshold value to obtain the Cu-Mo-S nanowire. Here nitrogen is used as shielding gas. Optionally, a quartz boat with powder placed therein is arranged in a tube furnace, the temperature is programmed to 800 ℃ at a temperature rising rate of 5 ℃/min under a nitrogen atmosphere, and the temperature is maintained for 5 hours, so that the Cu-Mo-S nanowire is obtained. Nanowires refer to one-dimensional structures that are confined below 100 nanometers in the lateral direction (without confinement in the longitudinal direction). Cu doping does not change Mo 2 C-MoS 2 Is a feature of (3). As shown in FIG. 3 and FIG. 4, the Cu-Mo-S nanowire has a linear structure and a molecular formula of Cu 1.8 Mo 6 S 8 。
Molybdenum-based compounds have an outer electron structure similar to platinum and thus play an important role in the study of electrocatalyst Hydrogen Evolution Reactions (HER). MoS (MoS) 2 Is being studied extensively because it still shows stable and good HER activity in an acidic environment. MoS (MoS) 2 The main strategy of modification is to reduce the d track center position of Mo, weaken the Mo-H bond energy and improve the desorption capacity of hydrogen so as to improve the electrolysis efficiency. Electrocatalyst Hydrogen Evolution Reaction (HER) refers to the electrochemical generation of hydrogen using a catalyst.
The invention provides a preparation method of a Cu-Mo-S nanowire, which comprises the step of doping Mo with Cu 2 C-MoS 2 Changing the electronic structure of the outer layer of Mo, and changing the MoS of semiconductor property 2 The Cu-Mo-S compound which is converted into a Shevirel phase (Chevrel phase) with metallic property is beneficial to greatly improving the HER performance. In the technical scheme defined by the invention, the cheap transition metal material is used for replacing the noble metal material with high cost and limited yield, thereby being beneficial to reducing the production cost of the electrolyzed water. In addition, in the preparation process of the Cu-Mo-S nanowire, the electronic structure of the Mo outer layer is changed by Cu doped with Mo sulfide, so that the performance is improved, the catalytic activity is improved, and the electrolysis energy consumption is reduced.
In one embodiment according to the invention, the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate is equal to the amount of the substance of trithiocyanic acid. Copper nitrate and ammonium molybdate are metal salts. The amount of the substance of the metal salt is equal to the amount of the substance of the trithiocyanic acid, i.e. the equimolar ratio of the metal salt to the trithiocyanic acid, to ensure that the Cu-Mo-S compound of the Sheffir phase can be prepared. The Cu-Mo-S compound is Cu-Mo-S nanowire.
In one embodiment according to the invention, the amount of the substance of copper nitrate is 5% to 70% of the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate. By controlling the percentage of copper nitrate in relation to the amount of metal salt material, it is ensured that a Cu-Mo-S compound of the Sheffier phase can be prepared.
In one embodiment according to the invention, the amount of the substance of copper nitrate is equal to the amount of the substance of ammonium molybdate. By setting the copper nitrate and ammonium molybdate to equimolar amounts, this mode of preparation performs best, at 0.5mol H 2 SO 4 The current density in the solution was 71.4mA/cm 2 . The current density is a vector unit and represents the current intensity and the flowing direction. The current density is equal to the electric quantity passing through a certain unit area in unit time; the direction of the current density is the normal vector of the corresponding section per unit area, and the direction is determined by the direction of positive charges through this section. Alternatively, the voltage is 400mV. Alternatively, the ratio of the amount of the substance of copper nitrate, the amount of the substance of ammonium molybdate, and the amount of the substance of trithiocyanic acid is 1:1:2.
in one embodiment according to the present invention, as shown in fig. 2, the specific steps of the preparation method of Cu-Mo-S nanowire include:
s202, dissolving copper nitrate, ammonium molybdate and trithiocyanic acid in deionized water, adding an aniline solution after ultrasonic stirring for a first time threshold, wherein the volume ratio of the deionized water to the aniline solution is 50:1, forming a first mixed solution. Copper nitrate is an inorganic chemical with the chemical formula Cu (NO) 3 ) 2 . Ammonium molybdate is an inorganic salt of the formula (NH 4 ) 2 MoO 4 . Trithiocyanate, i.e. cyanuric acid, with molecular formula C 3 H 3 N 3 S 3 . Deionized water refers to pure water from which impurities in ionic form have been removed. Copper nitrate, ammonium molybdate and trithiocyanic acid in a certain proportion are dissolved in deionized water. Alternatively, the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate, with thiocyanideThe amount of acid material is equal. Alternatively, the amount of the substance of copper nitrate is 5% to 70% of the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate. Alternatively, the amount of the substance of copper nitrate is equal to the amount of the substance of ammonium molybdate. Further, the solution is stirred by ultrasound for a first time threshold before the aniline solution is added. Ultrasonic stirring is ultrasonic stirring, and the solution is stirred by using high shear force generated by cavitation of ultrasonic waves. Aniline is also known as aminobenzene, which is an organic compound with a chemical formula of C 6 H 7 N is a colorless oily liquid. Dissolving aniline in organic solvent such as ethanol or diethyl ether to obtain aniline solution. The volume ratio of deionized water to aniline solution is controlled to ensure that the Cu-Mo-S compound of the Sheffier phase can be prepared. Alternatively, 0.05mmol (millimole) of copper nitrate, 0.95mmol of ammonium molybdate and 1mmol of trithiocyanic acid are dissolved in 50mL of deionized water, and after stirring ultrasonically for 30min, 1mL of aniline solution is added. Alternatively, 0.5mmol (millimole) of copper nitrate, 0.5mmol of ammonium molybdate and 1mmol of trithiocyanic acid are dissolved in 50mL of deionized water, and after stirring ultrasonically for 30min, 1mL of aniline solution is added. Alternatively, 0.5mmol (millimole) of copper nitrate, 0.5mmol of ammonium molybdate and 1mmol of trithiocyanic acid are dissolved in 50mL of deionized water, and after stirring ultrasonically for 30min, 1mL of aniline solution is added. The method comprises the steps of mixing copper nitrate, ammonium molybdate, trithiocyanic acid, deionized water and an aniline solution to obtain a first mixed solution;
s204, the pH value of the first mixed solution is adjusted dropwise through dilute hydrochloric acid until the pH value is 3.5, so that a second mixed solution is formed. Optionally, the pH of the first mixed solution is adjusted dropwise with dilute hydrochloric acid until the pH is 3.5. The purpose of this step is to adjust the acid-base value of the first mixed solution to an acidic condition and obtain a second mixed solution. The acid-base value of the first mixed solution is quantitatively calibrated to be 3.5, so that the reaction condition of chemical substances can be ensured, and the Cu-Mo-S compound of the Sheffier phase is prepared in the subsequent steps;
and S206, standing the second mixed solution at the first temperature threshold for a second time threshold to obtain a precipitate. The precipitate here is a Cu-Mo complex. And (3) placing the mixed solution in a baking oven at 50 ℃, and standing for 12 hours to obtain the Cu-Mo complex. The purpose of this step is to chemically react the chemical substances in the second mixed solution under acidic conditions and at a first temperature threshold to obtain a Cu-Mo complex. The first three steps are precursor preparation steps. The precursor is in a form of existence before the target product is obtained, and mostly exists in the form of organic and inorganic complexes or mixtures;
and S208, cleaning the precipitate for a plurality of times through ethanol and deionized water, and drying the precipitate for a third time threshold under a second temperature threshold. The purpose of the multiple cleaning and drying is to remove extraneous variables. Optionally, washing the precipitate with ethanol and deionized water for multiple times, and drying at 60deg.C for 4 hr;
and S210, grinding the dried precipitate to obtain powder. The powder obtained after grinding has larger contact area, which is beneficial to chemical reaction in the subsequent steps. Optionally, the ground powder is placed in a quartz boat. The quartz boat is also called quartz glass, and has the characteristic of high temperature resistance;
and S212, heating the powder to a third temperature threshold at a constant speed at a first speed threshold under the nitrogen atmosphere, and maintaining a fourth time threshold to obtain the Cu-Mo-S nanowire. Here nitrogen is used as shielding gas. Optionally, a quartz boat with powder placed therein is arranged in a tube furnace, the temperature is programmed to 800 ℃ at a temperature rising rate of 5 ℃/min under a nitrogen atmosphere, and the temperature is maintained for 5 hours, so that the Cu-Mo-S nanowire is obtained. Nanowires refer to one-dimensional structures that are confined below 100 nanometers in the lateral direction (without confinement in the longitudinal direction). Cu doping does not change Mo 2 C-MoS 2 Is a feature of (3). As shown in FIG. 3 and FIG. 4, the Cu-Mo-S nanowire has a linear structure and a molecular formula of Cu 1.8 Mo 6 S 8 。
In another embodiment, the precipitate is a cu—mo complex. Complexes, also known as coordination compounds, are a class of compounds having a characteristic chemical structure formed by the binding of a central atom to a molecule or ion surrounding it (called a ligand), either entirely or in part, by a coordination bond. The Cu-Mo complex is separated out in the form of a precipitate, so that the Cu-Mo complex is conveniently processed in the subsequent step to obtain the Cu-Mo-S compound of the Sheffier phase.
In another embodiment, the first time threshold is 25min to 35min. By controlling the ultrasonic stirring time, on one hand, the ultrasonic stirring time is prevented from being too short, and the copper nitrate, ammonium molybdate and trithiocyanic acid can be fully mixed in deionized water to carry out chemical reaction; on the other hand, the ultrasonic stirring is avoided for too long, which is beneficial to improving the preparation efficiency.
In another embodiment, the first time threshold is 30 minutes. The time of ultrasonic stirring is controlled by setting the first time threshold to 30min, so that copper nitrate, ammonium molybdate and trithiocyanic acid can be fully mixed in deionized water for chemical reaction, and the preparation efficiency can be improved.
In another embodiment, the second time threshold is 11h to 13h. By controlling the standing time of the second mixed solution, on one hand, the excessively short standing time is avoided, and the yield of the required sediment is ensured; on the other hand, the long standing time is avoided, and the preparation efficiency is improved.
In another embodiment, the second time threshold is 12h. By setting the second time threshold to 12 hours, the standing time of the second mixed solution is controlled, the yield of the desired precipitate can be ensured, and the production efficiency can also be improved.
In another embodiment, the third time threshold is 3h to 5h. By controlling the drying time of the precipitate, on one hand, the excessively short drying time is avoided, the irrelevant factors are removed, and the preparation of the Cu-Mo-S compound of the Sheffier phase in the subsequent step is ensured; on the other hand, the method avoids overlong drying time and is beneficial to improving the preparation efficiency.
In another embodiment, the third time threshold is 4h. The third time threshold is set to 4 hours, so that the drying time of the precipitate is controlled, irrelevant factors are removed, the preparation of the Cu-Mo-S compound of the Sheffier phase in the subsequent step is ensured, and the preparation efficiency can be improved.
In another embodiment, the fourth time threshold is 4h to 6h. By controlling the high-temperature sintering time of the powder, on one hand, the high-temperature sintering time of the powder is prevented from being too short, and the Cu-Mo-S compound of the Sheffier phase is ensured to be prepared in the subsequent step; on the other hand, the method avoids overlong high-temperature sintering time of the powder, and is beneficial to improving the preparation efficiency.
In another embodiment, the fourth time threshold is 5h. By setting the fourth time threshold to 5 hours and controlling the high-temperature sintering time of the powder, it is possible to ensure that the Cu-Mo-S compound of the Sheffier phase is prepared in the subsequent step, and also to improve the preparation efficiency.
In another embodiment, the first temperature threshold is 50 ℃. By setting the first temperature threshold to 50 ℃ and controlling the ambient temperature when the second mixed solution is left to stand, the yield of the desired precipitate can be ensured.
In another embodiment, the second temperature threshold is 60 ℃. By setting the second temperature threshold to 60 ℃, the drying temperature of the precipitate is controlled, which is beneficial to removing extraneous factors, and ensuring that the Cu-Mo-S compound of the Sheffier phase is prepared in the subsequent step.
In another embodiment, the third temperature threshold is 800 ℃. By setting the third temperature threshold to 800 ℃ and controlling the highest temperature of the powder at high temperature sintering, it is possible to ensure that the Cu-Mo-S compound of the Sheffier phase is produced in the subsequent step.
In another embodiment, the first speed threshold is 4 ℃/min to 6 ℃/min. By controlling the heating rate of high-temperature sintering, on one hand, the over-fast heating is avoided, and the temperature programming is realized; on the other hand, the temperature rise is avoided from being too slow, and the preparation efficiency is improved.
In another embodiment, the first speed threshold is 5 ℃/min. And setting the first speed threshold to be 5 ℃ per minute, programming to be heated to 800 ℃ at the heating rate of 5 ℃ per minute, and sintering the powder at a high temperature after 5 hours to form the Cu-Mo-S nanowire.
In one embodiment according to the present invention, the Cu-Mo-S nanowire is fabricated by the method of fabricating the Cu-Mo-S nanowire in any of the embodiments described above. As shown in FIG. 3 and FIG. 4, the Cu-Mo-S nanowire has a linear structure and a molecular formula of Cu 1.8 Mo 6 S 8 。
According to embodiments of the Cu-Mo-S nanowire and the method of preparing the same of the present invention, mo is doped with Cu 2 C-MoS 2 Changing the electronic structure of the outer layer of Mo, and changing the MoS of semiconductor property 2 The transformation into a Shefler phase Cu-Mo-S compound with metallic properties is advantageous for greatly improving its HER performance, as shown in FIG. 5, an X-ray diffraction pattern (XRD) for characterizing the transformation process of the crystalline phase, the abscissa of which is twice the incident angle of the X-ray, namely 2Theta, which can be called as diffraction angle, the ordinate of XRD represents the intensity after diffraction, and MoS can be seen from FIG. 5 2 Peak position values of the synthesized Cu-Mo-S compound and standard card (i.e. theoretical data, such as MoS in FIG. 5 2 Standard and Cu 1.8 Mo 6 S 8 Standard) one corresponding to demonstrate that MoS2 is converted to a Cu-Mo-S compound with a Chevrel phase structure by doping with Cu element. In the technical scheme defined by the invention, the cheap transition metal material is used for replacing the noble metal material with high cost and limited yield, thereby being beneficial to reducing the production cost of the electrolyzed water. In addition, in the preparation process of the Cu-Mo-S nanowire, the electronic structure of the Mo outer layer is changed by Cu doped with Mo sulfide, so that the performance is improved, the catalytic activity is improved, and the electrolysis energy consumption is reduced.
In the present invention, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more, unless expressly defined otherwise. The terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; "coupled" may be directly coupled or indirectly coupled through intermediaries. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "left", "right", "front", "rear", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or units referred to must have a specific direction, be constructed and operated in a specific direction, and thus should not be construed as limiting the present invention.
In the description of the present specification, the terms "one embodiment," "some embodiments," "particular embodiments," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (21)
1. A method for preparing a Cu-Mo-S nanowire, comprising:
dissolving copper nitrate, ammonium molybdate and trithiocyanic acid in deionized water, ultrasonically stirring for a first time threshold, and then adding an aniline solution to form a first mixed solution;
dropwise adjusting the acid-base value of the first mixed solution through dilute hydrochloric acid until the first mixed solution is acidic to form a second mixed solution;
standing the second mixed solution for a second time threshold at the first temperature threshold to obtain a precipitate;
washing the precipitate for multiple times through ethanol and deionized water, and drying the precipitate at a second temperature threshold for a third time threshold;
grinding the dried precipitate to obtain powder;
and heating the powder to a third temperature threshold at a constant speed at a first speed threshold under the nitrogen atmosphere, and maintaining a fourth time threshold to obtain the Cu-Mo-S nanowire.
2. The method of producing Cu-Mo-S nanowires according to claim 1, wherein the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate is equal to the amount of the substance of trithiocyanic acid.
3. The method of producing Cu-Mo-S nanowires according to claim 1, characterized in that the amount of the substance of copper nitrate is 5 to 70% of the sum of the amount of the substance of copper nitrate and the amount of the substance of ammonium molybdate.
4. A method of producing Cu-Mo-S nanowires according to any of the claims 1 to 3, characterized in that the amount of the substance of copper nitrate is equal to the amount of the substance of ammonium molybdate.
5. A method for preparing a Cu-Mo-S nanowire according to any one of claims 1 to 3, wherein the dissolving of copper nitrate, ammonium molybdate and trithiocyanic acid in deionized water, ultrasonic stirring for a first time threshold, adding an aniline solution to form a first mixed solution, specifically:
dissolving the copper nitrate, the ammonium molybdate and the trithiocyanic acid in the deionized water, adding the aniline solution after ultrasonic stirring for the first time threshold, wherein the volume ratio of the deionized water to the aniline solution is 50:1, forming the first mixed solution.
6. A method of preparing Cu-Mo-S nanowires according to any of the claims 1 to 3, characterized in that said adjusting the acid-base value of said first mixed solution drop-wise by dilute hydrochloric acid until said first mixed solution is acidic, forming a second mixed solution, in particular:
the pH value of the first mixed solution is adjusted dropwise through the dilute hydrochloric acid until the pH value is 3.5, so that the second mixed solution is formed.
7. A method of preparing a Cu-Mo-S nanowire according to any one of the claims 1 to 3, characterized in that the precipitate is a Cu-Mo complex.
8. A method of producing Cu-Mo-S nanowires according to any of the claims 1 to 3, characterized in that the first time threshold is 25min to 35min.
9. The method of producing Cu-Mo-S nanowires of claim 8, wherein the first time threshold is 30min.
10. A method of producing Cu-Mo-S nanowires according to any of the claims 1 to 3, characterized in that the second time threshold is 11h to 13h.
11. The method of producing Cu-Mo-S nanowires of claim 10, wherein the second time threshold is 12h.
12. A method of producing Cu-Mo-S nanowires according to any of the claims 1 to 3, characterized in that the third time threshold is 3h to 5h.
13. The method of producing Cu-Mo-S nanowires of claim 12, wherein the third time threshold is 4h.
14. A method of producing Cu-Mo-S nanowires according to any of the claims 1 to 3, characterized in that the fourth time threshold is 4 to 6h.
15. The method of preparing Cu-Mo-S nanowires of claim 14, wherein the fourth time threshold is 5h.
16. A method of producing Cu-Mo-S nanowires according to any of the claims 1 to 3, characterized in that the first temperature threshold is 50 ℃.
17. A method of producing Cu-Mo-S nanowires according to any of the claims 1 to 3, characterized in that the second temperature threshold is 60 ℃.
18. A method of producing Cu-Mo-S nanowires according to any of the claims 1 to 3, characterized in that the third temperature threshold is 800 ℃.
19. A method of preparing a Cu-Mo-S nanowire according to any one of the claims 1 to 3, characterized in that the first speed threshold is 4 ℃/min to 6 ℃/min.
20. The method of preparing Cu-Mo-S nanowires of claim 19, wherein the first speed threshold is 5 ℃/min.
21. A Cu-Mo-S nanowire manufactured by the method of manufacturing a Cu-Mo-S nanowire according to any one of the claims 1 to 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310625613.3A CN116375088A (en) | 2023-05-30 | 2023-05-30 | Cu-Mo-S nanowire and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310625613.3A CN116375088A (en) | 2023-05-30 | 2023-05-30 | Cu-Mo-S nanowire and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116375088A true CN116375088A (en) | 2023-07-04 |
Family
ID=86963711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310625613.3A Pending CN116375088A (en) | 2023-05-30 | 2023-05-30 | Cu-Mo-S nanowire and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116375088A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835044A (en) * | 2017-02-15 | 2017-06-13 | 苏州思创源博电子科技有限公司 | A kind of preparation method of molybdenum bisuphide semiconductor film material |
| CN108565128A (en) * | 2018-04-02 | 2018-09-21 | 桂林电子科技大学 | A kind of preparation method and application of Cu-Mo-S nuclear-shell structured nano-composite materials |
-
2023
- 2023-05-30 CN CN202310625613.3A patent/CN116375088A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106835044A (en) * | 2017-02-15 | 2017-06-13 | 苏州思创源博电子科技有限公司 | A kind of preparation method of molybdenum bisuphide semiconductor film material |
| CN108565128A (en) * | 2018-04-02 | 2018-09-21 | 桂林电子科技大学 | A kind of preparation method and application of Cu-Mo-S nuclear-shell structured nano-composite materials |
Non-Patent Citations (1)
| Title |
|---|
| KASINATH OJHA等: ""Synthesis of Chevrel phase (Cu1.8Mo6S8) in composite with molybdenum carbide for hydrogen evolution reactions"", 《BULL. MATER. SCI.》, vol. 41, pages 2 - 3 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106865506B (en) | It is a kind of to form controllable nickel cobalt compound nano line and the preparation method and application thereof | |
| CN106498430A (en) | Low energy consumption electrochemistry hydrogen generating system based on dual-functional nanometer array electrode | |
| Ahmad et al. | Facile synthesis of Pr-doped ZnO photocatalyst using sol–gel method and its visible light photocatalytic activity | |
| Farooq et al. | Review on metals and metal oxides in sustainable energy production: progress and perspectives | |
| CN112875755B (en) | Preparation method of bismuth tungstate nano powder | |
| CN106622318A (en) | Layered composite photocatalyst using bimetallic nanoparticles as heterojunctions and preparation method thereof | |
| Xu et al. | Cu 2 ZnSnS 4 and Cu 2 ZnSn (S 1− x Se x) 4 nanocrystals: room-temperature synthesis and efficient photoelectrochemical water splitting | |
| CN108807986A (en) | A kind of preparation method of mineral yellow micro-nano structure crystal | |
| CN112680741A (en) | Preparation method and application of ruthenium-doped cobalt phosphide electrocatalyst | |
| KR20200048454A (en) | The method of generating oxygen vacancies in nickel-cobalt oxide for oxygen reduction reaction and nickel-cobalt oxide thereby | |
| CN106944120B (en) | A kind of carbonitride/graphene oxide/(040) crystal face pucherite hetero-junctions and its preparation method and application | |
| CN109772294B (en) | Preparation method of tetragonal phase BiVO4 film with p-type conductivity, obtained product and application | |
| Nishi et al. | Low-Overpotential Electrochemical Water Oxidation Catalyzed by CuO Derived from 2 nm-Sized Cu2 (NO3)(OH) 3 Nanoparticles Generated by Laser Ablation at the Air–Liquid Interface | |
| Sarilmaz et al. | Ternary and quaternary thiospinel nanocrystals with adjustable compositions: effects of Band-Gaps and nanostructures on Visible-Light-Driven photocatalytic H2 evolution | |
| Li et al. | Fabrication approach impact on solar-to-hydrogen evolution of protonic titanate-derived nano-TiO2 | |
| Balu et al. | Fabrication of Bi2O3/bismuth titanates modified with metal–organic framework-in2S3/CdIn2S4 materials for electrocatalytic H2 production and its photoactivity | |
| Balgude et al. | Metal oxides for high-performance hydrogen generation by water splitting | |
| CN116375088A (en) | Cu-Mo-S nanowire and preparation method thereof | |
| JP4051433B2 (en) | Zinc oxide polycrystalline tube | |
| CN115449835A (en) | Preparation method of carbon fiber-loaded copper-nickel alloy nanoparticle nitrate transamination catalyst | |
| CN110142062B (en) | Symmetrical ship anchor-shaped three-dimensional cobalt-tungsten polyoxometalate crystalline catalytic material and preparation method thereof | |
| CN110241433A (en) | The controllable AgCuO of size2Nano material and its preparation and application | |
| Raimundo et al. | Nickel oxide nanocatalyst obtained by a combined sol-gel and hydrothermal method for oxygen evolution reaction | |
| CN101423200B (en) | Novel preparation method of transient metal sulfide alloy | |
| CN109529837A (en) | A kind of preparation method of leaf of bamboo shape nano cupric oxide visible light catalyst |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230704 |