CN110684990A - Molybdenum phosphide nano material and preparation method and application thereof - Google Patents
Molybdenum phosphide nano material and preparation method and application thereof Download PDFInfo
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- CN110684990A CN110684990A CN201810726215.XA CN201810726215A CN110684990A CN 110684990 A CN110684990 A CN 110684990A CN 201810726215 A CN201810726215 A CN 201810726215A CN 110684990 A CN110684990 A CN 110684990A
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- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 83
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 50
- 239000011733 molybdenum Substances 0.000 claims abstract description 50
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 239000002071 nanotube Substances 0.000 claims abstract description 38
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 29
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 17
- 239000012459 cleaning agent Substances 0.000 claims description 16
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 6
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- -1 medical treatment Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- 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
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a molybdenum phosphide nano material and a preparation method and application thereof. The molybdenum phosphide nano material comprises an array consisting of molybdenum phosphide nanotubes. The preparation method comprises the following steps: (1) taking a molybdenum raw material as an anode, and electrolyzing the molybdenum raw material and a cathode in an electrolyte containing ammonium fluoride to obtain electrolyzed molybdenum; the solvent in the ammonium fluoride electrolyte contains glycerol; (2) heating the electrolyzed molybdenum obtained in the step (1) in an inert gas environment to obtain modified molybdenum; (3) and (3) mixing the modified molybdenum obtained in the step (2) with a phosphorus source, and carrying out heating reaction to obtain the molybdenum phosphide nano material. The molybdenum phosphide nano material is used as a catalyst in the field of electrocatalysis. The molybdenum phosphide nano material provided by the invention has the advantages of novel appearance, large specific surface area, many active sites and excellent catalytic performance; the preparation method provided by the invention is simple to operate, short in flow, low in cost and good in industrial production prospect.
Description
Technical Field
The invention relates to the field of a preparation method of a nanometer material, and particularly relates to a molybdenum phosphide nanometer material and a preparation method and application thereof.
Background
Energy is an important basis upon which humans are dependent for survival and development. However, as non-renewable energy sources are gradually exhausted, the demand of human beings for renewable clean energy sources is increasing. Hydrogen is widely concerned by people for the reasons of cleanness, no pollution and the like. Among various hydrogen production methods, hydrogen production by electrolyzing water is one of the currently important means. In which process an electrocatalyst with high catalytic activity is usually required. Metal phosphide has excellent thermal conductivity and thermal stability, and thus is widely used in the fields of lithium batteries, electronic materials, medical treatment, catalysts, and the like. In the reported literature, the preparation of molybdenum phosphide is mainly focused on powder samples, and the molybdenum phosphide is beneficial to recycling in the application process.
CN107999105A discloses a preparation method of a molybdenum phosphide hydrogen evolution catalyst with a porous rod-like morphology structure, which comprises the following steps: weighing a certain amount of soluble ammonium molybdate and ammonium dihydrogen phosphate, dissolving in deionized water, magnetically stirring to completely dissolve the solution to form a clear transparent solution, adding a certain amount of clean and dry absorbent cotton, and continuously stirring for a certain time to ensure that the absorbent cotton fully absorbs the solution as much as possible; then transferring the molybdenum phosphide precursor to an oven for drying, putting the dried product into a muffle furnace, and preserving the heat at a certain temperature for a certain time to obtain a molybdenum phosphide precursor; and finally, putting the precursor into a tubular furnace, preserving the heat for a certain time at a certain temperature in a reducing atmosphere, and cooling to room temperature to obtain the molybdenum phosphide hydrogen evolution catalyst with the rod-shaped porous morphology structure.
CN101898141A discloses a preparation method of a molybdenum phosphide catalyst and an application of the molybdenum phosphide catalyst in methane carbon dioxide reforming, and the specific scheme is as follows: (1) mixing ammonium molybdate, diammonium hydrogen phosphate, citric acid and waterAccording to the following steps: weighing at the mass ratio of 1.0: 0.87: 0-3.6: 50-70, stirring, adding into a high-pressure kettle at the temperature of 363-; (2) cooling and drying; (3)623 and 923K for 3-8 hours; (4) cooling, placing into a tube, and measuring with flow rate of 20-100 ml/min-1H2Reducing, heating from 473K to 923--1Keeping the temperature for 2 hours; at H2Rapidly cooling to room temperature, and adding 1.0 vol% O2Argon passivation for 8-12 hours.
However, the molybdenum phosphide catalyst obtained by the method has complicated experimental steps and is not suitable for the application of hydrogen production by water electrolysis.
Therefore, the development of the molybdenum phosphide nano material with larger specific surface area and better catalytic performance has great significance to the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a molybdenum phosphide nano material and a preparation method and application thereof. The molybdenum phosphide (MoP) nano material provided by the invention is novel in appearance, simple in preparation process, high in catalytic activity of the product and beneficial to recycling.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a molybdenum phosphide nanomaterial comprising an array of molybdenum phosphide nanotubes.
In the invention, the array structure formed by the molybdenum phosphide nanotubes enables the molybdenum phosphide nano-material provided by the invention to have a large specific surface area and more active sites compared with molybdenum phosphide nano-materials with other structures, such as molybdenum phosphide nano-sheets or molybdenum phosphide nano-rods, so that the catalytic performance of the molybdenum phosphide nano-material provided by the invention is more excellent.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferred technical scheme of the invention, the molybdenum phosphide nano material is an array consisting of molybdenum phosphide nanotubes. Namely, when the molybdenum phosphide nano-material is a molybdenum phosphide nano-tube array, the molybdenum phosphide nano-material has more excellent specific surface area and catalytic activity.
Preferably, in the molybdenum phosphide nanomaterial, the molybdenum phosphide nanotube has an outer diameter of 60nm to 120nm, such as 60nm, 80nm, 90nm, 100nm, 110nm or 120nm, but the molybdenum phosphide nanotube is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the molybdenum phosphide nanomaterial has an inner diameter of molybdenum phosphide nanotubes of 30nm to 60nm, such as 30nm, 40nm, 45nm, 50nm, 55nm or 60nm, but the inner diameter is not limited to the recited value, and other values not recited in the range of the inner diameter are also applicable.
Preferably, in the molybdenum phosphide nanomaterial, the thickness of the tube wall of the molybdenum phosphide nanotube is 20nm to 30nm, such as 20nm, 22nm, 24nm, 26nm, 28nm or 30nm, but the thickness is not limited to the recited value, and other values not recited in the range of the value are also applicable.
In a second aspect, the present invention provides a method for preparing a molybdenum phosphide nanomaterial as described in the first aspect, wherein the method comprises the following steps:
(1) taking a molybdenum raw material as an anode, and electrolyzing the molybdenum raw material and a cathode in an electrolyte containing ammonium fluoride to obtain electrolyzed molybdenum;
wherein, in the electrolyte containing ammonium fluoride, a solvent used contains glycerol;
(2) heating the electrolyzed molybdenum obtained in the step (1) in an inert gas environment to obtain modified molybdenum;
(3) and (3) mixing the modified molybdenum obtained in the step (2) with a phosphorus source, and carrying out heating reaction to obtain the molybdenum phosphide nano material.
In the preparation method provided by the invention, the electrolysis step in the step (1) is firstly carried out, and molybdenum and ammonium fluoride (NH) in the electrolysis process are utilized4F) Changing the shape of the molybdenum raw material into a tubular shape; and (3) improving the crystallinity and stability of the molybdenum which becomes tubular after electrolysis through the heating modification process in the step (2), so that the molybdenum can not be dissolved in use(ii) a And finally, heating and calcining the modified molybdenum and a phosphorus source to obtain a molybdenum phosphide nanotube structure, thereby forming the molybdenum phosphide nano material provided by the invention.
As a preferable technical solution of the present invention, in the step (1), the molybdenum raw material is a molybdenum sheet.
Preferably, in step (1), the purity of molybdenum in the molybdenum raw material is above 99%, such as 99.1%, 99.2%, 99.3%, 99.4%, or 99.5%.
Preferably, in the step (1), the electrolyte containing ammonium fluoride is composed of ammonium fluoride and a solvent.
Preferably, in the ammonium fluoride-containing electrolyte solution of step (1), the concentration of ammonium fluoride is 0.1mol/L to 1.0mol/L, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.36mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, or 1.0mol/L, etc., but not limited to the enumerated values, and other non-enumerated values within the range of values are equally applicable, preferably 0.36 mol/L.
Preferably, in the ammonium fluoride-containing electrolyte in step (1), the solvent is a mixed solvent of water and glycerol.
Preferably, the volume ratio of glycerol to water in the mixed solvent of water and glycerol is 5:1 to 10:1, for example, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but not limited to the recited values, and other values not recited in the above range are also applicable.
Preferably, in step (1), the cathode is a noble metal electrode.
Preferably, the noble metal electrode is a platinum electrode.
Preferably, in step (1), the voltage for electrolysis is 10V-50V dc voltage, such as 10V, 15V, 20V, 25V, 30V, 35V, 40V, 45V or 50V, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, in step (1), the electrolysis time is 0.5 hours to 2 hours, such as 0.5 hours, 1 hour, 1.5 hours, or 2 hours, but not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferred embodiment of the present invention, the step (1) further comprises the step (1'): before electrolysis, the molybdenum raw material is subjected to ultrasonic cleaning, then is washed by water, and finally is dried in a nitrogen environment to obtain the purified molybdenum raw material.
Preferably, in step (1'), the ultrasonic cleaning is performed in an ultrasonic cleaner.
Preferably, in step (1'), the cleaning agent for ultrasonic cleaning is acetone and/or ethanol. In the present invention, the acetone and/or ethanol means: the cleaning agent can be acetone, ethanol or a mixture of acetone and ethanol. The ethanol used as the cleaning agent is preferably absolute ethanol.
Preferably, in step (1'), the ultrasonic frequency of the ultrasonic cleaning is 50kHz to 100kHz, for example, 50kHz, 60kHz, 70kHz, 80kHz, 90kHz or 100kHz, etc., but is not limited to the recited values, and other values not recited within the range of the recited values are also applicable.
Preferably, in step (1'), the ultrasonic cleaning is performed for 5 minutes to 50 minutes, such as 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, or 50 minutes, but not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
In a preferred embodiment of the present invention, in the step (2), the inert gas includes nitrogen and/or argon. In the present invention, the nitrogen and/or argon means: the nitrogen gas may be used, the argon gas may be used, or a combination of the nitrogen gas and the argon gas may be used.
Preferably, in step (2), the heating temperature is 50 ℃ to 500 ℃, such as 50 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 350 ℃ to 450 ℃.
Preferably, in step (2), the heating time is 60 minutes to 120 minutes, such as 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, or 120 minutes, but not limited to the recited values, and other values within the range are equally applicable, preferably 90 minutes.
As a preferable embodiment of the present invention, the step (2) further includes: soaking the molybdenum after electrolysis in the step (1) in an immersion liquid before heating, and drying in an inert gas environment.
Preferably, the immersion fluid comprises ethanol.
Preferably, the soaking time is 10 minutes to 25 minutes, such as 10 minutes, 15 minutes, 20 minutes, 25 minutes, etc., but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 15 minutes.
Preferably, the inert gas comprises nitrogen and/or argon. In the present invention, the nitrogen and/or argon means: the nitrogen gas may be used, the argon gas may be used, or a combination of the nitrogen gas and the argon gas may be used.
As a preferred technical scheme of the invention, in the step (3), the phosphorus source comprises sodium hypophosphite (NaH)2PO2) Preferably sodium hypophosphite monohydrate (NaH)2PO2·H2O)。
Preferably, in step (3), the mass ratio of the phosphorus source to the modified molybdenum of step (2) is from 5:2 to 5:3, such as 5:2, 5:2.2, 5:2.4, 5:2.6, 5:2.8 or 5:3, but not limited to the recited values, and other values not recited in this range are equally applicable, preferably 5: 2.4.
Preferably, the heating reaction is carried out in a tube furnace.
Preferably, the temperature of the heating reaction is 200 ℃ to 1000 ℃, such as 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable, preferably 600 ℃.
Preferably, the heating reaction is carried out for a time period of 1 hour to 2 hours, such as 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, or 2 hours, but not limited to the recited values, and other values not recited within the range of the recited values are also applicable.
Preferably, step (3) further comprises: after the heating reaction, the obtained reaction product is naturally cooled to 20-30 ℃.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1') performing ultrasonic cleaning on the molybdenum raw material in an ultrasonic cleaner for 15 minutes by using acetone as a cleaning agent, performing ultrasonic cleaning on the molybdenum raw material in the ultrasonic cleaner for 15 minutes by using ethanol as a cleaning agent, washing with water, and finally drying in a nitrogen environment to obtain a purified molybdenum raw material;
(1) electrolyzing the purified molybdenum raw material in the step (1') by using a 10V-50V direct current voltage in an ammonium fluoride-containing electrolyte for 0.5-2 hours by using a platinum electrode as a cathode to obtain electrolyzed molybdenum;
the electrolyte containing ammonium fluoride consists of ammonium fluoride and a solvent, wherein the concentration of the ammonium fluoride in the electrolyte containing ammonium fluoride is 0.36mol/L, the solvent is a mixed solvent of water and glycerol, and the volume ratio of the glycerol to the water is 5:1-10: 1;
(2) soaking the electrolyzed molybdenum obtained in the step (1) in ethanol for 15 minutes, drying in a nitrogen environment, and heating at the temperature of 350-450 ℃ for 90 minutes in the nitrogen environment to obtain modified molybdenum;
(3) mixing the modified molybdenum obtained in the step (2) with sodium hypophosphite monohydrate, carrying out heating reaction in a tubular furnace at the reaction temperature of 600 ℃ for 1-2 h, and naturally cooling the obtained reaction product to 20-30 ℃ after the heating reaction to obtain the molybdenum phosphide nano material;
wherein the mass ratio of the sodium hypophosphite monohydrate to the modified molybdenum in the step (2) is 5: 2.4.
In a third aspect, the present invention provides a use of the molybdenum phosphide nanomaterial as described in the first aspect, as a catalyst in the field of electrocatalysis.
Compared with the prior art, the invention has the following beneficial effects:
(1) the molybdenum phosphide nano-tube in the molybdenum phosphide nano-material provided by the invention forms a regular array, and the nano-material has the advantages of large specific surface area, more active sites, good catalytic performance, and high catalytic activity of 10mAcm-2Exhibits a very low overpotential, which may be as low as about 270 mV.
(2) The preparation method provided by the invention is simple to operate, short in flow, low in cost and good in industrial production prospect.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of a molybdenum phosphide nanomaterial prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction (XRD) spectrum of the molybdenum phosphide nano-material prepared in example 1 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) picture of a molybdenum phosphide nanomaterial prepared in example 3 of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) picture of the molybdenum phosphide nanomaterial prepared in comparative example 1;
FIG. 5 is a Scanning Electron Microscope (SEM) picture of the molybdenum phosphide nanomaterial prepared in comparative example 2.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
The embodiment provides a preparation method of a molybdenum phosphide nano material, which comprises the following specific steps:
(1') taking a molybdenum sheet with the purity of 99%, sequentially adopting acetone and ethanol to respectively clean for 15 minutes, flushing with deionized water, and drying in a nitrogen environment to obtain a purified molybdenum sheet;
(1) will contain NH4And adding glycerol into the aqueous solution of the F, and uniformly stirring. Wherein NH4F is 4.0g (the concentration is 0.36mol/L), the volume of the deionized water is 30ml, and the volume of the glycerol is 270 ml; taking the solution as electrolyte, taking the molybdenum sheet purified in the step (1') as an anode and a Pt electrode as a cathode, applying 40V voltage to two ends of the cathode and the anode, and electrifying for 1h to obtain electrolyzed molybdenum;
(2) heating the electrolyzed molybdenum in the step (1) for 90min at 350 ℃ in an inert gas environment to obtain modified molybdenum;
(3) mixing the modified molybdenum obtained in the step (2) with 0.25g of NaH2PO2·H2And (3) putting the O together into a tube furnace, heating to 700 ℃, preserving the heat for 1h, and naturally cooling to room temperature (25 ℃) to obtain the molybdenum phosphide nano material. Wherein, NaH2PO2·H2The mass ratio of O to the modified molybdenum in the step (2) is 5: 2.4.
The molybdenum phosphide nano-material obtained in the embodiment is an array consisting of molybdenum phosphide nanotubes, the outer diameter of each molybdenum phosphide nanotube is 80-120nm, the inner diameter of each molybdenum phosphide nanotube is 40-60nm, and the thickness of each molybdenum phosphide nanotube is 20-30 nm.
The molybdenum phosphide nano material provided by the embodiment is 10mAcm-2The overpotential of the catalyst was 270 mV.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the molybdenum phosphide nanomaterial prepared in this example, from which it can be seen that the nanotubes are arranged neatly and have uniform pore sizes.
FIG. 2 is the X-ray diffraction (XRD) spectrum of the molybdenum phosphide nano-material prepared in this example, from which it can be seen that the prepared material is molybdenum phosphide.
Example 2
The embodiment provides a preparation method of a molybdenum phosphide nano material, which comprises the following specific steps:
(1') taking a molybdenum sheet with the purity of 99%, ultrasonically cleaning the molybdenum sheet in an ultrasonic cleaner for 15 minutes by using acetone as a cleaning agent, ultrasonically cleaning the molybdenum sheet in the ultrasonic cleaner for 15 minutes by using absolute ethyl alcohol as a cleaning agent, washing the molybdenum sheet with deionized water, and drying the molybdenum sheet in a nitrogen environment to obtain a purified molybdenum sheet;
(1) NH contained thereafter4Adding glycerol into the aqueous solution F, and uniformly stirring. Wherein NH4F is 4.0g (the concentration is 0.36mol/L), the volume of the deionized water is 30ml, and the volume of the glycerol is 270 ml; taking the solution as electrolyte, taking the molybdenum sheet purified in the step (1') as an anode and a Pt electrode as a cathode, applying 35V voltage to two ends of the cathode and the anode, and electrifying for 1h to obtain electrolyzed molybdenum;
(2) heating the electrolyzed molybdenum in the step (1) for 90min at 350 ℃ in an inert gas environment to obtain modified molybdenum;
(3) mixing the modified molybdenum obtained in the step (2) with 0.25g of NaH2PO2·H2And (3) putting the O together into a tube furnace, heating to 700 ℃, preserving the heat for 1h, and naturally cooling to room temperature (25 ℃) to obtain the molybdenum phosphide nano material. Wherein, NaH2PO2·H2The mass ratio of O to the modified molybdenum in the step (2) is 5: 2.4.
The molybdenum phosphide nano-material obtained in the embodiment is an array consisting of molybdenum phosphide nanotubes, the outer diameter of each molybdenum phosphide nanotube is 85nm-105nm, the inner diameter of each molybdenum phosphide nanotube is 45nm-55nm, and the thickness of each molybdenum phosphide nanotube is 20nm-25 nm.
The molybdenum phosphide nano material provided by the embodiment is 10mAcm-2The overpotential of the catalyst was 280 mV.
Example 3
The embodiment provides a preparation method of a molybdenum phosphide nano material, which comprises the following specific steps:
(1') taking a molybdenum sheet with the purity of 99%, ultrasonically cleaning the molybdenum sheet for 25 minutes at 50kHz in an ultrasonic cleaner by using acetone as a cleaning agent, ultrasonically cleaning the molybdenum sheet for 25 minutes at 100kHz in the ultrasonic cleaner by using absolute ethyl alcohol as a cleaning agent, flushing the molybdenum sheet by using deionized water, and drying the molybdenum sheet in a nitrogen environment to obtain a purified molybdenum sheet;
(1) NH to be contained4And adding glycerol into the aqueous solution of F, and uniformly stirring. Wherein NH4F is 4.5g (the concentration is 0.41mol/L), the volume of the deionized water is 45ml, and the volume of the glycerol is 255 ml; taking the solution as electrolyte, taking the molybdenum sheet purified in the step (1') as an anode and a Pt electrode as a cathode, applying 40V voltage to two ends of the cathode and the anode, and electrifying for 0.5h to obtain electrolyzed molybdenum;
(2) soaking the electrolyzed molybdenum obtained in the step (1) in ethanol for 15 minutes, drying in a nitrogen environment, and heating at 50 ℃ for 120min in the nitrogen environment to obtain modified molybdenum;
(3) mixing the modified molybdenum obtained in the step (2) with NaH2PO2·H2And (3) putting the O together into a tube furnace, heating to 500 ℃, preserving the heat for 1.5h, and naturally cooling to room temperature to obtain the molybdenum phosphide nano material.
The molybdenum phosphide nano-material obtained in the embodiment is an array consisting of molybdenum phosphide nanotubes, the outer diameter of each molybdenum phosphide nanotube is 60nm-110nm, the inner diameter of each molybdenum phosphide nanotube is 30nm-50nm, and the thickness of each molybdenum phosphide nanotube is 20nm-30 nm.
The molybdenum phosphide nano material provided by the embodiment is 10mAcm-2The overpotential of the catalyst is 276 mV.
Fig. 3 is a Scanning Electron Microscope (SEM) image of the molybdenum phosphide nanomaterial prepared in this example, from which it can be seen that the pore size is relatively uniform.
Example 4
The embodiment provides a preparation method of a molybdenum phosphide nano material, which comprises the following specific steps:
(1') taking a molybdenum sheet with the purity of 99%, ultrasonically cleaning the molybdenum sheet in an ultrasonic cleaner at 75kHz for 2.5 minutes by using acetone as a cleaning agent, ultrasonically cleaning the molybdenum sheet in the ultrasonic cleaner at 75kHz for 2.5 minutes by using absolute ethyl alcohol as a cleaning agent, flushing the molybdenum sheet by using deionized water, and drying the molybdenum sheet in a nitrogen environment to obtain a purified molybdenum sheet;
(1) NH to be contained4And adding glycerol into the aqueous solution of F, and uniformly stirring. Wherein NH4F is 1.5g (the concentration is 0.1mol/L), the volume of the deionized water is 45ml, and the volume of the glycerol is 360 ml; taking the solution as electrolyte, taking the molybdenum sheet purified in the step (1') as an anode and a Pt electrode as a cathode, applying 25V voltage to the two ends of the cathode and the anode, and electrifying for 2h to obtain electrolyzed molybdenum;
(2) soaking the electrolyzed molybdenum obtained in the step (1) in ethanol for 25 minutes, drying in a nitrogen environment, and heating at 500 ℃ for 60 minutes in the nitrogen environment to obtain modified molybdenum;
(3) mixing the modified molybdenum obtained in the step (2) with NaH2PO2·H2And (3) putting the O together into a tube furnace, heating to 200 ℃, preserving the heat for 2h, and naturally cooling to room temperature to obtain the molybdenum phosphide nano material. Wherein, NaH2PO2·H2The mass ratio of O to the modified molybdenum in the step (2) is 5:2.
The molybdenum phosphide nano-material obtained in the embodiment is an array consisting of molybdenum phosphide nanotubes, the outer diameter of each molybdenum phosphide nanotube is 60nm-80nm, the inner diameter of each molybdenum phosphide nanotube is 30nm-50nm, and the thickness of each molybdenum phosphide nanotube is 20nm-30 nm.
The molybdenum phosphide nano material provided by the embodiment is 10mAcm-2The overpotential of the catalyst is 283 mV.
Example 5
The embodiment provides a preparation method of a molybdenum phosphide nano material, which comprises the following specific steps:
(1') taking a molybdenum sheet with the purity of 99%, ultrasonically cleaning the molybdenum sheet for 10 minutes at 75kHz in an ultrasonic cleaner by using acetone as a cleaning agent, ultrasonically cleaning the molybdenum sheet for 10 minutes at 75kHz in the ultrasonic cleaner by using absolute ethyl alcohol as a cleaning agent, flushing the molybdenum sheet with deionized water, and drying the molybdenum sheet in a nitrogen environment to obtain a purified molybdenum sheet;
(1) NH to be contained4And adding glycerol into the aqueous solution of F, and uniformly stirring. Wherein NH4F is 4g (the concentration is 0.22mol/L), the volume of the deionized water is 45ml, and the volume of the glycerol is 450 ml; taking the solution as electrolyte, taking the molybdenum sheet purified in the step (1') as an anode and a Pt electrode as a cathode, applying a voltage of 45V to two ends of the cathode and the anode, and electrifying for 1h to obtain electrolyzed molybdenum;
(2) soaking the electrolyzed molybdenum obtained in the step (1) in ethanol for 10 minutes, drying in a nitrogen environment, and heating at 350 ℃ for 90 minutes in the nitrogen environment to obtain modified molybdenum;
(3) mixing the modified molybdenum obtained in the step (2) with NaH2PO2·H2And (3) putting the O together into a tube furnace, heating to 600 ℃, preserving the heat for 1.5h, and naturally cooling to room temperature to obtain the molybdenum phosphide nano material. Wherein, NaH2PO2·H2The mass ratio of O to the modified molybdenum in the step (2) is 5: 3.
The molybdenum phosphide nano-material obtained in the embodiment is an array consisting of molybdenum phosphide nanotubes, the outer diameter of each molybdenum phosphide nanotube is 100nm-120nm, the inner diameter of each molybdenum phosphide nanotube is 30nm-60nm, and the thickness of each molybdenum phosphide nanotube is 20nm-30 nm.
The molybdenum phosphide nano material provided by the embodiment is 10mAcm-2The overpotential of the catalyst is 286 mV.
Comparative example 1
The specific process of this comparative example is as in example 1 except that in step (1) of this comparative example, glycerol is not used in the electrolyte and ethylene glycol is used instead.
A Scanning Electron Microscope (SEM) picture of the molybdenum phosphide nanomaterial prepared in this comparative example is shown in fig. 4, from which it can be seen that the product of this comparative example was formed without the formed molybdenum phosphide nanotubes.
Comparative example 2
The specific process of this comparative example was as in example 1 except that NH was not used in the electrolyte in step (1) of this comparative example4F。
The desired morphology was not obtained in this comparative example. The Scanning Electron Microscope (SEM) picture of the molybdenum phosphide nanomaterial prepared by the comparative example is shown in FIG. 5, and it can be seen from the SEM picture that the molybdenum phosphide nanomaterial prepared by the comparative example does not have an array structure at all.
It can be known from the above examples and comparative examples that the molybdenum phosphide nanomaterial provided by this example has a large specific surface area, many active sites and good catalytic performance. The comparative example did not adopt the scheme of the present invention, and thus the effects of the present invention could not be obtained.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The molybdenum phosphide nano material is characterized by comprising an array consisting of molybdenum phosphide nanotubes.
2. The molybdenum phosphide nanomaterial of claim 1, wherein the molybdenum phosphide nanomaterial is an array consisting of molybdenum phosphide nanotubes;
preferably, in the molybdenum phosphide nano material, the outer diameter of the molybdenum phosphide nano tube is 60nm-120 nm;
preferably, in the molybdenum phosphide nano material, the inner diameter of the molybdenum phosphide nano tube is 30nm-60 nm;
preferably, in the molybdenum phosphide nano material, the thickness of the tube wall of the molybdenum phosphide nanotube is 20nm-30 nm.
3. The method for preparing molybdenum phosphide nanomaterial according to claim 1 or 2, wherein the method comprises the steps of:
(1) taking a molybdenum raw material as an anode, and electrolyzing the molybdenum raw material and a cathode in an electrolyte containing ammonium fluoride to obtain electrolyzed molybdenum;
wherein, in the electrolyte containing ammonium fluoride, a solvent used contains glycerol;
(2) heating the electrolyzed molybdenum obtained in the step (1) in an inert gas environment to obtain modified molybdenum;
(3) and (3) mixing the modified molybdenum obtained in the step (2) with a phosphorus source, and carrying out heating reaction to obtain the molybdenum phosphide nano material.
4. The method according to claim 3, wherein in the step (1), the molybdenum raw material is a molybdenum sheet;
preferably, in the step (1), the purity of molybdenum in the molybdenum raw material is more than 99%;
preferably, in the step (1), the electrolyte containing ammonium fluoride consists of ammonium fluoride and a solvent;
preferably, in the electrolyte containing ammonium fluoride in the step (1), the concentration of the ammonium fluoride is 0.1mol/L-1.0mol/L, and is preferably 0.36 mol/L;
preferably, in the electrolyte containing ammonium fluoride in the step (1), the solvent is a mixed solvent of water and glycerol;
preferably, in the mixed solvent of water and glycerol, the volume ratio of glycerol to water is 5:1-10: 1;
preferably, in step (1), the cathode is a noble metal electrode;
preferably, the noble metal electrode is a platinum electrode;
preferably, in the step (1), the voltage of the electrolysis is 10V-50V direct current voltage;
preferably, in the step (1), the electrolysis time is 0.5 to 2 hours.
5. The production method according to claim 3 or 4, characterized in that, in the step (1), the method further comprises the step (1'): before electrolysis, carrying out ultrasonic cleaning on a molybdenum raw material, then washing with water, and finally drying in a nitrogen environment to obtain a purified molybdenum raw material;
preferably, in step (1'), the ultrasonic cleaning is performed in an ultrasonic cleaner;
preferably, in the step (1'), the cleaning agent for ultrasonic cleaning is acetone and/or ethanol;
preferably, in the step (1'), the ultrasonic frequency of the ultrasonic cleaning is 50kHz-100 kHz;
preferably, in step (1'), the time for the ultrasonic cleaning is 5 minutes to 50 minutes.
6. The method according to any one of claims 3 to 5, wherein in step (2), the inert gas comprises nitrogen and/or argon;
preferably, in step (2), the temperature of heating is 50-500 ℃, preferably 350-450 ℃;
preferably, in step (2), the heating time is 60 minutes to 120 minutes, preferably 90 minutes.
7. The method according to any one of claims 3-6, wherein step (2) further comprises: soaking the molybdenum after electrolysis in the step (1) in an immersion liquid before heating, and drying in an inert gas environment;
preferably, the infusion comprises ethanol;
preferably, the soaking time is 10 minutes to 25 minutes, preferably 15 minutes;
preferably, the inert gas comprises nitrogen and/or argon.
8. The method according to any one of claims 4 to 6, wherein in step (3), the phosphorus source comprises sodium hypophosphite, preferably sodium hypophosphite monohydrate;
preferably, in the step (3), the mass ratio of the phosphorus source to the modified molybdenum in the step (2) is 5:2-5:3, preferably 5: 2.4;
preferably, the heating reaction is carried out in a tube furnace;
preferably, the temperature of the heating reaction is 200-1000 ℃, preferably 600 ℃;
preferably, the heating reaction time is 1 hour to 2 hours;
preferably, step (3) further comprises: after the heating reaction, the obtained reaction product is naturally cooled to 20-30 ℃.
9. The method for preparing according to any one of claims 3 to 8, characterized in that it comprises the steps of:
(1') performing ultrasonic cleaning on the molybdenum raw material in an ultrasonic cleaner for 15 minutes by using acetone as a cleaning agent, performing ultrasonic cleaning on the molybdenum raw material in the ultrasonic cleaner for 15 minutes by using ethanol as a cleaning agent, washing with water, and finally drying in a nitrogen environment to obtain a purified molybdenum raw material;
(1) electrolyzing the purified molybdenum raw material in the step (1') by using a 10V-50V direct current voltage in an ammonium fluoride-containing electrolyte for 0.5-2 hours by using a platinum electrode as a cathode to obtain electrolyzed molybdenum;
the electrolyte containing ammonium fluoride consists of ammonium fluoride and a solvent, wherein the concentration of the ammonium fluoride in the electrolyte containing ammonium fluoride is 0.36mol/L, the solvent is a mixed solvent of water and glycerol, and the volume ratio of the glycerol to the water is 5:1-10: 1;
(2) soaking the electrolyzed molybdenum obtained in the step (1) in ethanol for 15 minutes, drying in a nitrogen environment, and heating at the temperature of 350-450 ℃ for 90 minutes in the nitrogen environment to obtain modified molybdenum;
(3) mixing the modified molybdenum obtained in the step (2) with sodium hypophosphite monohydrate, carrying out heating reaction in a tubular furnace at the reaction temperature of 600 ℃ for 1-2 h, and naturally cooling the obtained reaction product to 20-30 ℃ after the heating reaction to obtain the molybdenum phosphide nano material;
wherein the mass ratio of the sodium hypophosphite monohydrate to the modified molybdenum in the step (2) is 5: 2.4.
10. Use of molybdenum phosphide nanomaterial according to claim 1 or 2, wherein the molybdenum phosphide nanomaterial is used as a catalyst in the field of electrocatalysis.
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Application publication date: 20200114 |