CN111013635A - Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof - Google Patents
Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111013635A CN111013635A CN202010016209.2A CN202010016209A CN111013635A CN 111013635 A CN111013635 A CN 111013635A CN 202010016209 A CN202010016209 A CN 202010016209A CN 111013635 A CN111013635 A CN 111013635A
- Authority
- CN
- China
- Prior art keywords
- substrate
- nitrogen
- composite material
- molybdenum carbide
- doped carbon
- 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.)
- Granted
Links
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 94
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000000758 substrate Substances 0.000 title claims abstract description 56
- 239000002245 particle Substances 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 21
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 21
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 20
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 20
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- 239000005416 organic matter Substances 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 186
- 229910052759 nickel Inorganic materials 0.000 claims description 86
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 238000002347 injection Methods 0.000 claims description 49
- 239000007924 injection Substances 0.000 claims description 49
- 239000000126 substance Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- -1 nitrogen-containing organic compound Chemical class 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 239000002360 explosive Substances 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 62
- 239000000243 solution Substances 0.000 description 34
- 239000008367 deionised water Substances 0.000 description 33
- 229910021641 deionized water Inorganic materials 0.000 description 33
- 239000011259 mixed solution Substances 0.000 description 32
- 238000001816 cooling Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 30
- 239000012071 phase Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 21
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 17
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 17
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 17
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 16
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 238000004321 preservation Methods 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- DVOFYPFFCLHONS-UHFFFAOYSA-N sodium molybdate tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[O-][Mo]([O-])(=O)=O DVOFYPFFCLHONS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 208000012868 Overgrowth Diseases 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and a preparation method and application thereof, wherein the nitrogen-doped carbon nanotube is surrounded around molybdenum carbide particles and is coated on the surface of a substrate; the composite material is prepared by uniformly coating a molybdenum oxide precursor on a substrate by adopting a hydrothermal synthesis method, then carrying out high-temperature annealing on the molybdenum oxide precursor in a roasting furnace under an inert atmosphere, and introducing a nitrogenous organic matter into the roasting furnace in the high-temperature annealing process to carry out high-temperature pyrolysis reaction. The preparation process has the advantages of simple flow, easy operation, low cost, no use of flammable and explosive gases, improved catalytic performance of the obtained composite material, strong stability and large-scale application potential for the development of industrial electrolytic water catalysts.
Description
Technical Field
The invention relates to a composite material, in particular to a substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and a preparation method and application thereof.
Background
Molybdenum carbide is gray powder with metallic luster, and has the advantages of high melting point and hardness, good thermal stability and mechanical stability, excellent corrosion resistance and the like. In recent years, molybdenum carbide has a d-electron structure similar to that of noble metals such as platinum and is called as a 'noble metal-like catalyst', so that the molybdenum carbide becomes a research hotspot in the research field of novel inorganic catalytic materials, and shows high catalytic activity in reactions such as hydrodenitrogenation, hydrodesulfurization, selective hydrogenation, alkane isomerization, methane carbon dioxide reforming, water vapor conversion and the like.
The traditional synthesis method of molybdenum carbide is a gas-solid phase synthesis method, namely, molybdenum oxide is obtained by high-temperature carbonization in a methane/hydrogen mixed gas environment. The method relates to flammable and explosive gases such as methane, hydrogen and the like, and has high danger. Meanwhile, the preparation of highly dispersed molybdenum carbide nanostructures remains a challenge because the molybdenum carbide material has inevitable agglomeration or overgrowth during the high-temperature preparation process, so that the particle size of the synthesized molybdenum carbide is large (micrometer level), and the synthesized catalyst has "longitudinal difference".
In order to prepare the molybdenum carbide material with uniform appearance and high electrocatalytic activity, on one hand, molybdenum carbide and a conductive carbon nano material can be compounded to avoid the agglomeration of molybdenum carbide particles, thereby improving the exposure of active sites and the proceeding of electrochemical reaction; on the other hand, a carrier with a larger specific surface area can be provided for molybdenum carbide, a self-supporting electrode structure is prepared, and the phenomenon that particles are enlarged due to polymerization of molybdenum carbide is avoided, so that the electrolyte is favorably permeated, and the electron transmission is facilitated. However, most of the molybdenum carbide-based catalysts reported at present are prepared in the form of powders, which require relatively complicated preparation processes to be tested, and have poor mechanical properties, charge and mass transfer capabilities. Therefore, it is necessary for practical application to prepare a self-supported molybdenum carbide-based catalytic material which is easy to handle and has high catalytic performance, but the self-supported molybdenum carbide-based catalytic material is of little concern.
Disclosure of Invention
One of the purposes of the invention is to provide a substrate-supported nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The invention also aims to provide a preparation method of the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The invention also aims to provide the application of the substrate-supported nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material in the aspect of industrial electrolysis hydrogen evolution electrocatalysts.
One of the objects of the invention is achieved by:
a composite material with a substrate loaded with nitrogen-doped carbon nanotubes surrounding molybdenum carbide particles is disclosed, wherein the nitrogen-doped carbon nanotubes surround the molybdenum carbide particles and are coated on the surface of foamed nickel.
The diameter of the nitrogen-doped carbon nanotube is 40-60 nm, and preferably, the diameter of the nitrogen-doped carbon nanotube is about 50 nm.
The doping amount of nitrogen (the ratio of the molar amount of nitrogen atoms to the total molar amount of nitrogen and carbon atoms) in the nitrogen-doped carbon nanotube is 8-10%, preferably 9.3%; the mass ratio of the nitrogen-doped carbon nano tube to the molybdenum carbide is 8-17%.
The particle size of the molybdenum carbide particles is 200-400 nm.
The substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material is obtained by coating a molybdenum oxide precursor on a substrate, and introducing a nitrogen-containing organic matter into the molybdenum oxide precursor in a high-temperature annealing process under an inert atmosphere for a high-temperature pyrolysis reaction.
The second purpose of the invention is realized by the following steps:
a preparation method of a substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material comprises the following steps:
(a) coating a molybdenum oxide precursor on a substrate by adopting a hydrothermal synthesis method;
(b) and (b) carrying out high-temperature annealing on the molybdenum oxide precursor obtained in the step (a) in a roasting furnace in an inert atmosphere, and introducing a nitrogenous organic matter into the roasting furnace in the high-temperature annealing process to carry out high-temperature pyrolysis reaction, so as to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
In step (a), the substrate may be selected from substrate materials commonly used in the art, such as foamed nickel, nickel mesh, foamed iron, iron mesh, foamed nickel-iron alloy, and the like,more preferably, foamed nickel (2X 5 cm) is selected2）。
The hydrothermal synthesis method can adopt reaction temperature and reaction time known by a person skilled in the art, preferably, the reaction temperature is 80-150 ℃, and the reaction time is 12-24 hours; more preferably, the reaction temperature is 100 ℃, and the reaction time is 12-18 h.
The molybdenum oxide precursor can be synthesized using known raw materials and solvents, and preferably, a solution containing molybdenum ions is mixed with an anionic surfactant to obtain a reaction mixed solution.
Optionally, the solution containing molybdenum ions is a solution obtained by dissolving inorganic molybdate in an appropriate amount of deionized water, wherein the inorganic molybdate is sodium molybdate or ammonium molybdate.
Optionally, the anionic surfactant is sodium dodecyl sulfate or sodium dodecyl sulfate.
Specifically, sodium molybdate tetrahydrate is used as a raw material, deionized water is used as a solvent, the ratio of the sodium molybdate tetrahydrate to the deionized water is 4 mmol: 100 mL, and then 20mmol of sodium dodecyl sulfate is added into the solution to obtain a colorless transparent mixed solution.
When the substrate is coated with the molybdenum oxide precursor, the obtained reaction liquid is transferred into a reaction container, and the substrate is placed obliquely close to the wall and undergoes a hydrothermal synthesis reaction at a set temperature.
In step (b), the inert atmosphere is preferably nitrogen or argon.
The reaction temperature of the high-temperature pyrolysis is preferably 650-750 ℃, more preferably 700-750 ℃, and more preferably 700 ℃.
The pyrolysis time of the high-temperature pyrolysis is preferably 30-180 min, more preferably 60-120 min, and more preferably 120 min.
The nitrogen-containing organic matter is acetonitrile or pyridine, etc.
The introduction amount of the nitrogen-containing organic matter can be adjusted according to the amount of the molybdenum oxide precursor coated on the substrate; preferably, the nitrogen-containing organic substance is acetonitrile.
The nitrogen-containing organic matter is introduced into the roasting furnace in an injection mode, and preferably, the nitrogen-containing organic matter or the solution of the nitrogen-containing organic matter is injected into the roasting furnace at a specific injection speed; the injection speed v is 0< v ≤ 10 mL/h; more preferably, 3 mL/h.ltoreq.v.ltoreq.6 mL/h. The injection time may be the same as or different from the pyrolysis time of the pyrolysis.
The third purpose of the invention is realized by the following steps:
the substrate-supported nitrogen-doped carbon nanotube surrounds the molybdenum carbide particle composite material and is applied to the field of electrolytic water catalysts.
According to the invention, a substrate is loaded with a molybdenum oxide precursor, and a nitrogen-containing organic matter is introduced into the molybdenum oxide precursor for high-temperature pyrolysis reaction in the high-temperature annealing process under an inert atmosphere, so as to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material. In the high-temperature pyrolysis process, the molybdenum oxide is carbonized into molybdenum carbide under the high-temperature carbonization action of nitrogen-containing organic matters, and the growth of the nitrogen-doped carbon nano tube is realized under the catalysis action of the substrate iron/nickel. The nitrogen-doped carbon nanotubes in the obtained composite material surround the molybdenum carbide particles and are uniformly coated on the surface of the substrate, the nitrogen-doped carbon nanotubes have uniform diameter, the catalytic performance is improved, and the stability is strong.
The preparation process of the composite material is simple, the operation is easy, the cost is low, the large-scale production is easy to carry out, and the prepared composite material has excellent alkaline electro-catalysis performance and has the potential of large-scale application for the development of industrial electrolyzed water catalysts.
Drawings
FIG. 1 is an XRD spectrum of the sample prepared in examples 1-14 and a standard sample of molybdenum carbide and nickel simple substance.
Fig. 2 is an XRD spectrum of the sample prepared in comparative example 1 and a standard sample of molybdenum oxide and nickel simple substance.
Fig. 3 is an SEM image of the sample prepared in example 1.
Fig. 4 is a Raman graph of the samples prepared in example 1.
Fig. 5 is an XPS chart of a sample prepared in example 1.
FIG. 6 is a polarization curve of hydrogen production by alkaline electrolysis of water for samples prepared in examples 1 to 3 and comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and the reagents used in the examples are either analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the objects of the present invention.
Example 1
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized in the morphology structure and chemical components, and the obtained results are shown in figures 1 and 3-5. As can be seen from figure 1, the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS cards, and the foam nickel substrate is Ni 78-1049 phase. As can be seen from FIG. 3, the obtained composite material is a structure in which carbon nanotubes surround molybdenum carbide particles and are uniformly coated on nickel foam, and the diameter of the carbon nanotubes is about 50 nm. As can be seen in fig. 4, there is carbon present in the composite. As can be seen in fig. 5, there is an N-C bond in the composite, indicating that the carbon in the composite exists in a carbon-nitrogen doped form.
Comparative example 1
Will be 4mmol ammonium molybdate tetrahydrate is dissolved in 100 mL deionized water, and then 20mmol sodium dodecyl sulfate is added into the solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (the flow rate is 60 sccm), heating to 600 ℃ at the speed of 5 ℃/min, slowly injecting acetonitrile solution into the high-temperature tubular furnace through an injection pump at the injection speed of 5mL/h, keeping the temperature of the tubular furnace for 120min, and naturally cooling to room temperature to obtain the foamed nickel loaded molybdenum oxide composite material.
The prepared material was characterized for chemical composition, and the results are shown in fig. 2.
Example 2
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 650 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tubular furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tubular furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 3
4mmol of ammonium molybdate tetrahydrate are dissolved in 100 mL of deionized water, and then 20mmol of twelve ammonium molybdate tetrahydrate are added to the solutionSodium alkylsulfonate to give a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 750 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 4
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 3mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 5
4mmol of ammonium molybdate tetrahydrate are dissolved in 10To 0mL of deionized water, 20mmol of sodium dodecylsulfate was added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 6mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 6
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 10mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 7
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 30 min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 8
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (the flow rate is 60 sccm), heating to 700 ℃ at the speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at the injection speed of 5mL/h, keeping the temperature of the tube furnace for 60 min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 9
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 180 min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 10
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 6 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying the nickel foam for 12 h in vacuum at 60 ℃. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 11
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 12 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 12
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 100 ℃, reacting for 24h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying the nickel foam for 12 h in vacuum at 60 ℃. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 13
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 80 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 14
4mmol of ammonium molybdate tetrahydrate is dissolved in 100 mL of deionized water, and then 20mmol of sodium dodecyl sulfate is added to the above solution to obtain a colorless transparent mixed solution. Transferring the mixed solution into a reaction kettle, and simultaneously adding foamed nickel (2 x 5 cm)2) Placing the nickel foam obliquely against the wall, heating to 150 ℃, reacting for 18 h, then naturally cooling, taking out the nickel foam, washing the nickel foam clean with deionized water, and drying in vacuum at 60 ℃ for 12 h. The samples were placed in a tube furnace at N2And (at a flow rate of 60 sccm), heating to 700 ℃ at a speed of 5 ℃/min, slowly injecting an acetonitrile solution into the high-temperature tube furnace through an injection pump at an injection speed of 5mL/h, wherein the heat preservation time and the injection time of the tube furnace are both 120min, and naturally cooling to room temperature to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
The prepared material is characterized by chemical components, the obtained result is shown in figure 1, and it can be seen that the molybdenum carbide phase in the prepared composite material is matched with MoC 45-1015 of JCPDS card, and the foam nickel substrate is Ni 78-1049 phase.
Example 15
The substrate-supported nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material prepared in the examples 1-3 and the substrate-supported molybdenum oxide composite material prepared in the comparative example 1 are used for alkaline catalytic hydrogen evolution. The samples were electrochemically characterized using an electrochemical workstation and measured using a three-electrode system. The method comprises the following steps of using a mercury/mercury oxide electrode as a reference electrode, directly using a substrate loaded nitrogen-doped carbon nanotube surrounding molybdenum carbide particle composite material as a working electrode, and using 1M KOH as electrolyte. The electrochemical performance test is characterized by scanning a polarization curve, the scanning speed is 5 mV/s, and the test potential is converted into the standard hydrogen electrode potential.
The results are shown in FIG. 6, from which it can be seen that the sample obtained in example 1 has excellent electrocatalytic hydrogen production performance, particularly when the current density is 20mA/cm2The overpotential in 1M KOH was 246 mV, which was lower than that of the substrate-supported molybdenum oxide particle composite material prepared in example 2 (overpotential of 270 mV) and example 3 (overpotential of 260 mV) and the substrate-supported molybdenum oxide particle composite material prepared in comparative example 1 (overpotential of 350 mV). Therefore, the method can directly prepare the nitrogen-doped carbon nanotube/molybdenum carbide self-supporting electrode structure with excellent electro-catalytic performance.
Claims (10)
1. A substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material is characterized in that nitrogen-doped carbon nanotubes surround molybdenum carbide particles and are coated on the surface of a substrate; the mass ratio of the nitrogen-doped carbon nano tube to the molybdenum carbide is 8-17%.
2. The substrate-supported nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material of claim 1, wherein the nitrogen-doped carbon nanotube has a diameter of 40-60 nm.
3. The preparation method of the substrate-supported nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material as claimed in claim 1, characterized by comprising the following steps:
(a) coating a molybdenum oxide precursor on a substrate by adopting a hydrothermal synthesis method;
(b) and (b) performing high-temperature annealing on the molybdenum oxide precursor obtained in the step (a) in a roasting furnace in an inert atmosphere, and introducing a nitrogenous organic matter into the roasting furnace in the high-temperature annealing process to perform high-temperature pyrolysis reaction, so as to obtain the substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material.
4. The method for preparing the substrate-supported nitrogen-doped carbon nanotube surrounded molybdenum carbide particle composite material according to claim 3, wherein in the step (a), the substrate is foamed nickel, foamed iron or foamed iron-nickel alloy.
5. The preparation method of the substrate-supported nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material according to claim 3, wherein in the step (a), the reaction temperature of the hydrothermal synthesis method is 80-150 ℃, and the reaction time is 12-24 hours.
6. The method for preparing the substrate-supported nitrogen-doped carbon nanotube surrounded molybdenum carbide particle composite material according to claim 3, wherein in the step (b), the inert atmosphere is nitrogen or argon.
7. The method for preparing the substrate-supported nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material according to claim 3, wherein in the step (b), the temperature of the high-temperature pyrolysis reaction is 650-750 ℃.
8. The method for preparing the substrate-supported nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material according to claim 3, wherein in the step (b), the nitrogen-containing organic compound is acetonitrile, pyridine or the like.
9. The method for preparing the substrate-supported nitrogen-doped carbon nanotube surrounded molybdenum carbide particle composite material according to claim 8, wherein the nitrogen-containing organic substance is acetonitrile, which is introduced into the roasting furnace by injection, and the injection rate v is 0< v ≦ 10 mL/h.
10. The use of the substrate-supported nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material of claim 1 in the field of industrial electrolytic water catalysts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010016209.2A CN111013635B (en) | 2020-01-08 | 2020-01-08 | Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010016209.2A CN111013635B (en) | 2020-01-08 | 2020-01-08 | Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111013635A true CN111013635A (en) | 2020-04-17 |
| CN111013635B CN111013635B (en) | 2022-09-20 |
Family
ID=70198544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010016209.2A Active CN111013635B (en) | 2020-01-08 | 2020-01-08 | Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111013635B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111558387A (en) * | 2020-05-18 | 2020-08-21 | 湖南大学 | Molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution |
| CN113652709A (en) * | 2021-07-07 | 2021-11-16 | 暨南大学 | Nitrogen-doped carbon nanotube-coated nickel iron/molybdenum carbide and preparation method and application thereof |
| CN114592208A (en) * | 2022-03-21 | 2022-06-07 | 南通大学 | Preparation method of nitrogen-doped graphitized modified electrode |
| US11682531B1 (en) * | 2022-01-20 | 2023-06-20 | Imam Abdulrahman Bin Faisal University | Nanocomposite electrodes and method of preparation thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148959A (en) * | 2015-09-23 | 2015-12-16 | 厦门理工学院 | Molybdenum carbide-carbon nanotube composite particles and preparation method thereof |
| CN105964268A (en) * | 2016-05-17 | 2016-09-28 | 深圳市河科科技有限公司 | Metal catalyst preparation method and preparation method of carbon nanotube |
| CN107352543A (en) * | 2017-07-13 | 2017-11-17 | 东莞理工学院 | A kind of preparation method of molybdenum carbide micro-nano powder |
| CN108160077A (en) * | 2017-12-26 | 2018-06-15 | 江苏大学 | A kind of preparation method of nitrogen-doped carbon nanometer pipe coated metal ferrocobalt composite material |
| CN108265314A (en) * | 2018-02-07 | 2018-07-10 | 山东大学 | Bimetallic nitride nano wire decomposes water power catalyst, synthetic method and application entirely |
| CN109616669A (en) * | 2018-11-30 | 2019-04-12 | 上海师范大学 | Nanometer cobalt/nitrogen-doped carbon nanometer pipe composite material preparation method and applications |
| CN109894139A (en) * | 2019-04-28 | 2019-06-18 | 河北大学 | A kind of nitrogen-doped carbon cladding tungsten oxide nano composite material and preparation method and application |
-
2020
- 2020-01-08 CN CN202010016209.2A patent/CN111013635B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148959A (en) * | 2015-09-23 | 2015-12-16 | 厦门理工学院 | Molybdenum carbide-carbon nanotube composite particles and preparation method thereof |
| CN105964268A (en) * | 2016-05-17 | 2016-09-28 | 深圳市河科科技有限公司 | Metal catalyst preparation method and preparation method of carbon nanotube |
| CN107352543A (en) * | 2017-07-13 | 2017-11-17 | 东莞理工学院 | A kind of preparation method of molybdenum carbide micro-nano powder |
| CN108160077A (en) * | 2017-12-26 | 2018-06-15 | 江苏大学 | A kind of preparation method of nitrogen-doped carbon nanometer pipe coated metal ferrocobalt composite material |
| CN108265314A (en) * | 2018-02-07 | 2018-07-10 | 山东大学 | Bimetallic nitride nano wire decomposes water power catalyst, synthetic method and application entirely |
| CN109616669A (en) * | 2018-11-30 | 2019-04-12 | 上海师范大学 | Nanometer cobalt/nitrogen-doped carbon nanometer pipe composite material preparation method and applications |
| CN109894139A (en) * | 2019-04-28 | 2019-06-18 | 河北大学 | A kind of nitrogen-doped carbon cladding tungsten oxide nano composite material and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| GEON HEE LEE ET AL.: "Facile synthesis of nanostructured molybdenum carbide/nitrogendoped CNT-RGO composite via a modified urea glass route for efficient hydrogen evolution", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| WEI ZHAOQIAN ET AL.: "Supported Heterostructured MoC/Mo2C Nanoribbons and Nanoflowers as Highly Active Electrocatalysts for Hydrogen Evolution Reaction", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111558387A (en) * | 2020-05-18 | 2020-08-21 | 湖南大学 | Molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution |
| CN113652709A (en) * | 2021-07-07 | 2021-11-16 | 暨南大学 | Nitrogen-doped carbon nanotube-coated nickel iron/molybdenum carbide and preparation method and application thereof |
| CN113652709B (en) * | 2021-07-07 | 2023-01-17 | 暨南大学 | Nitrogen-doped carbon nanotube-coated nickel iron/molybdenum carbide and preparation method and application thereof |
| US11682531B1 (en) * | 2022-01-20 | 2023-06-20 | Imam Abdulrahman Bin Faisal University | Nanocomposite electrodes and method of preparation thereof |
| US11869714B2 (en) | 2022-01-20 | 2024-01-09 | Imam Abdulrahman Bin Faisal University | Method for making a nanocomposite electrode and supercapacitor |
| CN114592208A (en) * | 2022-03-21 | 2022-06-07 | 南通大学 | Preparation method of nitrogen-doped graphitized modified electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111013635B (en) | 2022-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Formation of lattice-dislocated bismuth nanowires on copper foam for enhanced electrocatalytic CO 2 reduction at low overpotential | |
| CN111013635B (en) | Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof | |
| CN107252700B (en) | Multi-metal phosphide nanotube catalyst with uniformly distributed catalytic centers and low-temperature preparation method | |
| CN109594101B (en) | Preparation method of porous carbon supported ruthenium catalyst | |
| CN112886024B (en) | Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst | |
| CN114032576B (en) | Preparation method of defect nanofiber carbon carrier coupled iron monatomic catalyst | |
| CN110904468B (en) | Cerium-doped tungsten phosphide submicron sphere composite material and preparation method and application thereof | |
| CN109616669B (en) | Preparation method and application of nano cobalt/nitrogen-doped carbon nanotube composite material | |
| CN110212204A (en) | A kind of efficient carbon nanosheet support type fuel cell positive electrode and its preparation method and application | |
| CN113036165A (en) | Nitrogen-sulfur doped defected carbon nanotube and preparation method thereof | |
| CN115896848A (en) | Nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst and preparation method and application thereof | |
| CN113659154A (en) | Carbon catalyst for cathode of alkaline fuel cell and preparation method thereof | |
| CN109546157A (en) | A kind of preparation method of copper, cobalt nitride and carbon In-situ reaction electrode | |
| CN110055556A (en) | Evolving hydrogen reaction catalyst and its preparation method and application | |
| CN115570143B (en) | Low-platinum high-entropy alloy nano-particle and preparation method and application thereof | |
| CN114566662B (en) | High-entropy intermetallic compound with ordered structure, preparation method thereof and application of high-entropy intermetallic compound as cathode catalyst of fuel cell | |
| CN116145193A (en) | Copper-based catalyst for electrocatalytic reduction of nitrate radical into ammonia and preparation method thereof | |
| CN114150339B (en) | Catalyst and preparation method and application thereof | |
| CN112593203B (en) | Preparation method and application of sulfur and/or nitrogen doped graphene nanosheet | |
| CN114142049A (en) | Preparation method and application of hollow carbon-based oxygen reduction electrocatalyst | |
| CN116377473B (en) | Nitrogen-doped hollow carbon nano-ring-loaded metal monoatomic material, preparation method and application thereof | |
| CN116675186B (en) | Ruthenium ditelluride nanotube, preparation method and application thereof | |
| CN114737216B (en) | Hydrogen evolution catalyst active material for electrolyzed water and preparation method thereof | |
| CN113426435B (en) | Carbon nanotube containing metal particles, metal organic frame material, electrode material, preparation method and application thereof | |
| CN114672843B (en) | Nickel nitride/ruthenium/nitrogen doped coal activated carbon composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |