CN106964362A - Metal molybdate/carbon composite nano-fiber and preparation method thereof and composite and its application - Google Patents
Metal molybdate/carbon composite nano-fiber and preparation method thereof and composite and its application Download PDFInfo
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- CN106964362A CN106964362A CN201710228674.0A CN201710228674A CN106964362A CN 106964362 A CN106964362 A CN 106964362A CN 201710228674 A CN201710228674 A CN 201710228674A CN 106964362 A CN106964362 A CN 106964362A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 239000002121 nanofiber Substances 0.000 title claims abstract description 73
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 50
- 239000002184 metal Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 83
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000002070 nanowire Substances 0.000 claims abstract description 54
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000003763 carbonization Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 15
- 239000008103 glucose Substances 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000005518 electrochemistry Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- -1 molybdic acid Salt Chemical class 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000835 fiber Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 2
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 15
- 230000005540 biological transmission Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- 239000004317 sodium nitrate Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005255 carburizing Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 4
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 3
- 229910039444 MoC Inorganic materials 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 235000012149 noodles Nutrition 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
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- MHLYOTJKDAAHGI-UHFFFAOYSA-N silver molybdate Chemical compound [Ag+].[Ag+].[O-][Mo]([O-])(=O)=O MHLYOTJKDAAHGI-UHFFFAOYSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B01J35/33—
-
- B01J35/40—
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- 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
Abstract
The invention provides a kind of preparation method of metal molybdate/carbon composite nano-fiber, comprise the following steps：A) tellurium nano-wire is mixed with glucose, hydrothermal carbonization reaction is carried out, obtains carbon coating tellurium nano-cable；B) carbon coating tellurium nano-cable is mixed with metal molybdate presoma, hydrothermal carbonization reaction is carried out, obtains metal molybdate/carbon composite nano-fiber.The invention provides a kind of method that magnanimity prepares metal molybdate and carbon composite nano-fiber, this method is simple and practical, and product purity is high, and fiber size is homogeneous and adjustable, and reaction cost is relatively low, it is easy to large-scale promotion.The composite nano fiber is subjected to high temperature cabonization processing, obtained material has good electrochemistry H2-producing capacity, it is thus only necessary to which 320mV and 365mV overpotential can respectively reach 10mA/cm2And 20mA/cm2Current density, be expected to be applied to water electrolysis hydrogen production field.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of metal molybdate/carbon composite nano-fiber and its
Preparation method and composite and its application.
Background technology
Metal molybdate is an important family in inorganic salt materials, because of its distinctive structure and physicochemical properties,
Get more and more people's extensive concerning.The advantages such as metal molybdate has high stability, excellent optics, chemical property so that its
Had a wide range of applications in every field.For example, application of the 1, molybdate in optics aspect, such as fluorophor, scintillator；2nd, molybdenum
Application of the hydrochlorate in environmental area, such as presses down mould, antibacterial and seawater inhibition；3rd, molybdate is widely used in energy storage neck
Domain, such as lithium ion battery, ultracapacitor；4th, molybdate is also widely used for catalytic field, and such as electro-catalysis, organic oxidation is anti-
It should wait.In recent years, developing rapidly with nanometer technology, countries in the world active development goes out various nano level metal molybdate materials
Material.In China, the reserves of molybdenum occupy the second in the world, and metal molybdenum is mainly for the production of various steel and alloy and molybdenum base semifinished product material.
The resources advantage of the high reserves of metal molybdenum how is utilized, new metal molybdate nano material is developed, promotes it in each production
The application in industry field, as current urgent problem to be solved.
Between past recent two decades, researcher is directed to grinding for various new metal molybdate nano materials always
Hair.The method for preparing molybdate wherein more commonly used is exactly liquid phase synthesizing method.Researcher synthesizes one using this method
The copper molybdate and molybdic acid indium of row metal molybdate, such as zero dimension, one-dimensional manganese molybdate and silver molybdate, two-dimentional nickel molybdate and molybdic acid
Cobalt, three-dimensional iron molybdate.It is difficult to control to however, this method has structure, sample size wider distribution and is difficult to scale
The shortcomings such as production.Solid-phase synthesis is also a kind of common method for preparing molybdate, but its energy consumption is higher and obtains
The specific surface area of sample is relatively low.Therefore, the metal molybdate that a kind of method magnanimity of cheap and simple prepares various high-quality is developed
Seem very urgent.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of metal molybdate/carbon composite nano-fiber
And preparation method thereof and composite and its application, metal molybdate/carbon composite nano-fiber size uniformity of preparation and can
Adjust.
The invention provides a kind of preparation method of metal molybdate/carbon composite nano-fiber, comprise the following steps：
A) tellurium nano-wire is mixed with glucose, hydrothermal carbonization reaction is carried out, obtains carbon coating tellurium nano-cable；
B) carbon coating tellurium nano-cable is mixed with metal molybdate presoma, hydrothermal carbonization reaction is carried out, obtains metal
Molybdate/carbon composite nano-fiber.
It is preferred that, the tellurium nano-wire is prepared in accordance with the following methods：
Sodium tellurite, polyvinylpyrrolidone, hydrazine hydrate, ammoniacal liquor are mixed in water, hydro-thermal reaction is carried out, obtains tellurium and receive
Rice noodles dispersion liquid；
The tellurium nano-wire dispersion liquid is centrifuged in organic solvent, tellurium nano-wire is obtained.
It is preferred that, the step A) in, the mol ratio of tellurium nano-wire and glucose is (0.05~0.2)：(5~20).
It is preferred that, the step A) in, the temperature of hydrothermal carbonization reaction is 160~200 DEG C, and the reaction time is 3~8h.
It is preferred that, the metal molybdate presoma is sodium molybdate and nitrate.
It is preferred that, the mol ratio of the sodium molybdate and nitrate is (0.5~3):(0.5~3).
It is preferred that, the nitrate is the one or more in cobalt nitrate, nickel nitrate and manganese nitrate.
It is preferred that, the step B) in, the temperature of hydrothermal carbonization reaction is 160~200 DEG C, and the reaction time is 8~48h.
The invention provides metal molybdate/carbon composite nano-fiber that a kind of above-mentioned preparation method is prepared.
The invention provides a kind of composite of nano-fibre supported particle, metal molybdenum prepared by above-mentioned preparation method
Hydrochlorate/carbon composite nano-fiber or above-mentioned metal molybdate/carbon composite nano-fiber are obtained through calcining.
It is preferred that, the temperature of the calcining is 300 DEG C~1200 DEG C.
The invention provides the composite of above-mentioned nano-fibre supported particle is produced from hydrogen field as catalyst in electrochemistry
Application.
Compared with prior art, the invention provides a kind of preparation method of metal molybdate/carbon composite nano-fiber, bag
Include following steps：A) tellurium nano-wire is mixed with glucose, hydrothermal carbonization reaction is carried out, obtains carbon coating tellurium nano-cable；B)
Carbon coating tellurium nano-cable is mixed with metal molybdate presoma, hydrothermal carbonization reaction is carried out, obtains metal molybdate/carbon multiple
Close nanofiber.The invention provides a kind of method that magnanimity prepares metal molybdate and carbon composite nano-fiber, this method letter
Single practical, product purity is high, and fiber size is homogeneous and adjustable, and reaction cost is relatively low, it is easy to large-scale promotion.By the composite Nano
Fiber carries out high temperature cabonization processing, and obtained material has good electrochemistry H2-producing capacity, it is thus only necessary to 320mV and 365mV
Overpotential can respectively reach 10mA/cm2And 20mA/cm2Current density, be expected to be applied to water electrolysis hydrogen production field.
Brief description of the drawings
Fig. 1 is the small multiple stereoscan photograph of the gained cobalt molybdate of embodiment 1 and carbon composite nano-fiber；
Fig. 2 is the big multiple stereoscan photograph of the gained cobalt molybdate of embodiment 1 and carbon composite nano-fiber；
Fig. 3 is the transmission electron microscope photo of the gained cobalt molybdate of embodiment 1 and carbon composite nano-fiber；
Fig. 4 is the transmission electron microscope photo of the gained cobalt molybdate of embodiment 2 and carbon composite nano-fiber；
Fig. 5 is the transmission electron microscope photo of the gained cobalt molybdate of embodiment 3 and carbon composite nano-fiber；
Fig. 6 is the transmission electron microscope photo of the gained cobalt molybdate of embodiment 4 and carbon composite nano-fiber；
Fig. 7 is the transmission electron microscope photo of the gained nickel molybdate of embodiment 5 and carbon composite nano-fiber；
Fig. 8 is the transmission electron microscope photo after the gained cobalt molybdate of embodiment 6 is carbonized with carbon composite nano-fiber at 500 DEG C；
Fig. 9 is the XRD curves after the gained cobalt molybdate of embodiment 6 is carbonized with carbon composite nano-fiber at 500 DEG C；
Figure 10 is the transmission electron microscope photo after the gained cobalt molybdate of embodiment 7 is carbonized with carbon composite nano-fiber at 900 DEG C；
Figure 11 is the XRD curves after the gained cobalt molybdate of embodiment 7 is carbonized with carbon composite nano-fiber at 900 DEG C；
Figure 12 is to be used to test electrochemistry production after the gained cobalt molybdate of embodiment 8 is carbonized with carbon composite nano-fiber at 900 DEG C
The polarization curve of hydrogen.
Embodiment
The invention provides a kind of preparation method of metal molybdate/carbon composite nano-fiber, comprise the following steps：
A) tellurium nano-wire is mixed with glucose, hydrothermal carbonization reaction is carried out, obtains carbon coating tellurium nano-cable；
B) carbon coating tellurium nano-cable is mixed with metal molybdate presoma, hydrothermal carbonization reaction is carried out, obtains metal
Molybdate/carbon composite nano-fiber.
The present invention is to the tellurium nano-wire and is not particularly limited, and can be general commercially available, or according to those skilled in the art
Prepared by well known method, present invention preferably employs following methods preparation：
Sodium tellurite, polyvinylpyrrolidone, hydrazine hydrate, ammoniacal liquor are mixed in water, hydro-thermal reaction is carried out, obtains tellurium and receive
Rice noodles dispersion liquid；
The tellurium nano-wire dispersion liquid is centrifuged in organic solvent, tellurium nano-wire is obtained.
Sodium tellurite and polyvinylpyrrolidone are preferably added in deionized water by the embodiment of the present invention, are mixed
Thing, then adds hydrazine hydrate and ammoniacal liquor.
In an embodiment of the present invention, the mass ratio of the sodium tellurite and polyvinylpyrrolidone be preferably (1.5~
7.5):(10~50), more preferably (2.5~6.5)：(15~45).The mass concentration of the sodium tellurite in aqueous is excellent
Elect 1.5g/L~7.5g/L, more preferably 2.5g/L~6.5g/L as.The quality of the polyvinylpyrrolidone in aqueous
Concentration is preferably 10g/L~50g/L, more preferably 15g/L~45g/L.The present invention is to the sodium tellurite and polyvinyl pyrrole
Alkanone and the charging sequence of water are not particularly limited.The present invention preferably mixes obtained sodium tellurite with polyvinylpyrrolidone
Thing is stirred, and stirring is mixed to get the mixed solution of clarification on magnetic stirring apparatus.The volume fraction of the hydrazine hydrate is preferably 2%
~6%, more preferably 4.0%~5.5%；The volume fraction of the ammoniacal liquor is preferably 4%~12%, more preferably 8%~
11%.
Then obtained mixed solution is transferred in reactor, put into baking oven, reacted certain time, obtain black
Tellurium nano-wire dispersion liquid.Wherein, the temperature of the reaction is preferably 160 DEG C~200 DEG C, more preferably 180 DEG C；The reaction
Time is preferably 2h~5h, more preferably 3h~4h.
The tellurium nano-wire dispersion liquid is centrifuged in organic solvent, you can obtain tellurium nano-wire.It is currently preferred, will
Obtained tellurium nano-wire dispersion liquid mixes centrifugation with excessive propanone, obtains tellurium nano-wire.The tellurium nano-wire dispersion liquid and acetone
Volume ratio be preferably 1:(2~5), more preferably 1：(3~4).The centrifugal rotational speed is preferably 10000~20000 revolutions per minute
Clock, more preferably 15000~18000 rpms.Centrifugation time is preferably 3~10 minutes, more preferably 5~8 minutes.
Then the tellurium nano-wire is mixed with glucose, carries out hydrothermal carbonization reaction, prepare carbon coating tellurium nano-cable.
It is preferred that, the tellurium nano-wire is re-dispersed into water, mixed with a certain amount of glucose.It is preferred that, it is described
The mol ratio of tellurium nano-wire and glucose is preferably (0.05~0.2)：(5~20), more preferably：(0.1~0.2)：(10~
15).The molar concentration of the tellurium nano-wire in aqueous is preferably 1.4mmol/L~5.6mmol/L, more preferably
2.8mmol/L~5.6mmol/L；Molar concentration of the glucose in the aqueous solution be preferably 140mmol/L~
560mmol/L, more preferably 280mmol/L~430mmol/L.The temperature of the carburizing reagent is preferably 160 DEG C~200 DEG C,
More preferably 180 DEG C；The time of the carburizing reagent is preferably 3h~8h, more preferably 4h~6h.The carburizing reagent it is molten
Liquid is preferably water or ethanol, more preferably water.
Then obtained carbon coating tellurium nano-cable solution is mixed with metal molybdate presoma, it is anti-by hydrothermal carbonization
Should be that can obtain the compound nanofiber of metal molybdate/carbon.
The metal molybdate presoma is preferably sodium molybdate and nitrate.The nitrate is preferably cobalt nitrate, nitric acid
One or more in nickel and manganese nitrate.
The mol ratio of the sodium molybdate and nitrate is preferably (0.5~3):(0.5~3), more preferably (1~2):(1~
2).The molar concentration of the sodium molybdate and nitrate in aqueous is respectively preferably 14mmol/L~84mmol/L respectively, more
Preferably 28mmol/L~56mmol/L；Nitrate in methods described is preferably cobalt nitrate, nickel nitrate or manganese nitrate, more excellent
Elect the one or more in cobalt nitrate or nickel nitrate as.The temperature of the hydrothermal carbonization reaction is preferably 160 DEG C~200
DEG C, more preferably 180 DEG C；The time of the carburizing reagent is preferably 8h~48h, more preferably 12h~24h.The hydro-thermal carbon
The solution for changing reaction is preferably water or ethanol, more preferably water.
Molybdate/carbon composite nano-fiber obtained above is preferably centrifuged, washed, in vacuum drying chamber by the present invention
Middle drying, obtains dry molybdate/carbon composite nano-fiber.Wherein, the centrifugation is separate mode commonly used in the art；Institute
It is mode of washing well known to those skilled in the art to state washing, and the present invention is not particularly limited to this.In the present invention, it is described dry
Dry temperature is preferably 50 DEG C~100 DEG C, more preferably 60 DEG C~90 DEG C.The time of the drying is preferably 4h~24h, more excellent
Elect 6h~20h, most preferably 12h~15h as.
Present invention also offers a kind of molybdate/carbon composite nano-fiber, it is prepared as described above obtaining.
Present invention also offers a kind of composite of nano-fibre supported particle, above-mentioned preparation method is prepared
Metal molybdate/carbon composite nano-fiber is obtained through calcining.
In an embodiment of the present invention, the calcining is preferably carried out under the atmosphere that protective gas is present；The protection
Property gas is preferably argon gas or nitrogen, more preferably argon gas.In the present invention, the temperature of the calcining be preferably 300 DEG C~
1200 DEG C, more preferably 500 DEG C~900 DEG C；The time of the calcining is preferably 1h~4h, more preferably 2h~3h.
Present invention also offers the composite of the nano-fibre supported particle obtained after above-mentioned high-temperature calcination, catalysis is used as
The application in hydrogen field is produced in agent in electrochemistry.
The electro-chemical test is determined under common three electrode conditions, and rotating disk electrode (r.d.e) supported catalyst is used as work
Make electrode, the wherein load capacity of catalyst is 0.5mg/cm2, platinized platinum is as to electrode, and saturated calomel electrode is used as reference electrode.
The electrolyte of electrochemical reaction is 1mol/L KOH solution, and the sweep speed of polarization curve is 2mV/s.
Test result indicates that, composite provided in an embodiment of the present invention in production hydrogen reacts, reaches as catalyst
10mA/cm2And 20mA/cm2Current density be only respectively necessary for 320mV and 365mV overpotential, in being current document report
Preferable numerical value.Had a good application prospect in electrochemical electrolysis water hydrogen preparation field.
In order to further illustrate the present invention, metal molybdate/carbon that the present invention is provided is combined with reference to embodiment and received
Rice fiber and preparation method thereof and composite and its application are described in detail.
Embodiment 1
(1) preparation of tellurium nano-wire dispersion liquid：920mg sodium tellurites and 10g polyvinylpyrrolidones are added to 320mL
In water, after stirring, 16.7mL hydrazine hydrates and 33.3mL ammoniacal liquor are added, 500mL polytetrafluoro is poured into after being stirred until homogeneous
In ethylene reaction kettle, 3h is reacted in 180 DEG C of baking ovens, you can obtain tellurium nano-wire dispersion liquid；
(2) preparation of carbon coating tellurium nano-cable：150mL tellurium nano-wires dispersion liquid is taken to be mixed with 450mL acetone,
Centrifuged 5 minutes under 15000 rpms of centrifugal speed, precipitated, the sediment of tellurium nano-wire is distributed to 350mL water
In, 20g glucose is added after being stirred until homogeneous, the mixed solution is transferred in 500mL ptfe autoclave,
5h is reacted in 180 DEG C of baking ovens, you can obtain carbon coating tellurium nano-cable dispersion liquid；
(3) preparation of metal cobalt molybdate and carbon composite nano-fiber：To 350mL carbon coatings tellurium nano-cable obtained above
20mmol sodium molybdates and 20mmol cobalt nitrates are sequentially added in dispersion liquid.500mL polytetrafluoroethylene (PTFE) is transferred to after stirring
In reactor, reacted in 180 DEG C of baking ovens after 12h, product is centrifuged, washed, dried in 60 DEG C of vacuum drying chambers
12h, you can obtain dry cobalt molybdate and carbon composite nano-fiber.
Obtained composite nano fiber is subjected to electronic microscope photos, as a result referring to Fig. 1~3.Fig. 1 is large-scale scanning electron
Microphotograph, it can be seen that the composite nano fiber of cobalt molybdate and carbon is one-dimentional structure and size uniformity.Fig. 2 is big multiple
Stereoscan photograph, it can be seen that fiber surface shows that cobalt molybdate nano particle is possible to be covered by fiber without any particle
The inside.Fig. 3 is transmission electron microscope photo, it can be seen that the diameter of fiber is about 90nm, and middle tellurium nano-wire template is still clear
It is clear visible.
Embodiment 2
(1) preparation of tellurium nano-wire dispersion liquid：920mg sodium tellurites and 10g polyvinylpyrrolidones are added to 320mL
In water, after stirring, 16.7mL hydrazine hydrates and 33.3mL ammoniacal liquor are added, 500mL polytetrafluoro is poured into after being stirred until homogeneous
In ethylene reaction kettle, 3h is reacted in 180 DEG C of baking ovens, you can obtain tellurium nano-wire dispersion liquid；
(2) preparation of carbon coating tellurium nano-cable：120mL tellurium nano-wires dispersion liquid is taken to be mixed with 450mL acetone,
Centrifuged 5 minutes under 15000 rpms of centrifugal speed, precipitated, the sediment of tellurium nano-wire is distributed to 350mL water
In, 20g glucose is added after being stirred until homogeneous, the mixed solution is transferred in 500mL ptfe autoclave,
5h is reacted in 180 DEG C of baking ovens, you can obtain carbon coating tellurium nano-cable dispersion liquid；
(3) preparation of metal cobalt molybdate and carbon composite nano-fiber：To 350mL carbon coatings tellurium nano-cable obtained above
20mmol sodium molybdates and 20mmol cobalt nitrates are sequentially added in dispersion liquid.500mL polytetrafluoroethylene (PTFE) is transferred to after stirring
In reactor, reacted in 180 DEG C of baking ovens after 12h, product is centrifuged, washed, dried in 60 DEG C of vacuum drying chambers
12h, you can obtain dry cobalt molybdate and carbon composite nano-fiber.
Obtained composite nano fiber is subjected to transmission electron microscope analysis, as a result referring to Fig. 4.It can be seen that the composite Nano is fine
Dimension size uniformity, surface are smooth without any particle, and middle tellurium nano-wire template is still clear.Due to reducing tellurium nano-wire
The consumption of template and other response parameters are unchanged, result in the diameter increase of nanofiber, about 130nm.
Embodiment 3
(1) preparation of tellurium nano-wire dispersion liquid：920mg sodium tellurites and 10g polyvinylpyrrolidones are added to 320mL
In water, after stirring, 16.7mL hydrazine hydrates and 33.3mL ammoniacal liquor are added, 500mL polytetrafluoro is poured into after being stirred until homogeneous
In ethylene reaction kettle, 3h is reacted in 180 DEG C of baking ovens, you can obtain tellurium nano-wire dispersion liquid；
(2) preparation of carbon coating tellurium nano-cable：80mL tellurium nano-wires dispersion liquid is taken to be mixed with 450mL acetone,
Centrifuged 5 minutes under 15000 rpms of centrifugal speed, precipitated, the sediment of tellurium nano-wire is distributed to 350mL water
In, 20g glucose is added after being stirred until homogeneous, the mixed solution is transferred in 500mL ptfe autoclave,
5h is reacted in 180 DEG C of baking ovens, you can obtain carbon coating tellurium nano-cable dispersion liquid；
(3) preparation of metal cobalt molybdate and carbon composite nano-fiber：To 350mL carbon coatings tellurium nano-cable obtained above
20mmol sodium molybdates and 20mmol cobalt nitrates are sequentially added in dispersion liquid.500mL polytetrafluoroethylene (PTFE) is transferred to after stirring
In reactor, reacted in 180 DEG C of baking ovens after 12h, product is centrifuged, washed, dried in 60 DEG C of vacuum drying chambers
12h, you can obtain dry cobalt molybdate and carbon composite nano-fiber.
Obtained composite nano fiber is subjected to transmission electron microscope analysis, as a result referring to Fig. 5.It can be seen that the composite Nano is fine
Dimension size uniformity, surface are smooth without any particle, and middle tellurium nano-wire template is still clear.Relative to embodiment 1~2,
The consumption of tellurium nano-wire template is further reduced, and the diameter of nanofiber further increases, about 150nm.
Embodiment 4
(1) preparation of tellurium nano-wire dispersion liquid：920mg sodium tellurites and 10g polyvinylpyrrolidones are added to 320mL
In water, after stirring, 16.7mL hydrazine hydrates and 33.3mL ammoniacal liquor are added, 500mL polytetrafluoro is poured into after being stirred until homogeneous
In ethylene reaction kettle, 3h is reacted in 180 DEG C of baking ovens, you can obtain tellurium nano-wire dispersion liquid；
(2) preparation of carbon coating tellurium nano-cable：50mL tellurium nano-wires dispersion liquid is taken to be mixed with 450mL acetone,
Centrifuged 5 minutes under 15000 rpms of centrifugal speed, precipitated, the sediment of tellurium nano-wire is distributed to 350mL water
In, 20g glucose is added after being stirred until homogeneous, the mixed solution is transferred in 500mL ptfe autoclave,
5h is reacted in 180 DEG C of baking ovens, you can obtain carbon coating tellurium nano-cable dispersion liquid；
(3) preparation of metal cobalt molybdate and carbon composite nano-fiber：To 350mL carbon coatings tellurium nano-cable obtained above
20mmol sodium molybdates and 20mmol cobalt nitrates are sequentially added in dispersion liquid.500mL polytetrafluoroethylene (PTFE) is transferred to after stirring
In reactor, reacted in 180 DEG C of baking ovens after 12h, product is centrifuged, washed, dried in 60 DEG C of vacuum drying chambers
12h, you can obtain dry cobalt molybdate and carbon composite nano-fiber.
Obtained composite nano fiber is subjected to transmission electron microscope analysis, as a result referring to Fig. 6.It can be seen that the composite Nano is fine
Dimension size uniformity, surface are smooth without any particle, and middle tellurium nano-wire template is still clear.Relative to embodiment 1~3,
The consumption of tellurium nano-wire template is further reduced, and the diameter of nanofiber further increases, about 180nm.
Embodiment 5
(1) preparation of tellurium nano-wire dispersion liquid：920mg sodium tellurites and 10g polyvinylpyrrolidones are added to 320mL
In water, after stirring, 16.7mL hydrazine hydrates and 33.3mL ammoniacal liquor are added, 500mL polytetrafluoro is poured into after being stirred until homogeneous
In ethylene reaction kettle, 3h is reacted in 180 DEG C of baking ovens, you can obtain tellurium nano-wire dispersion liquid；
(2) preparation of carbon coating tellurium nano-cable：50mL tellurium nano-wires dispersion liquid is taken to be mixed with 450mL acetone,
Centrifuged 5 minutes under 15000 rpms of centrifugal speed, precipitated, the sediment of tellurium nano-wire is distributed to 350mL water
In, 20g glucose is added after being stirred until homogeneous, the mixed solution is transferred in 500mL ptfe autoclave,
5h is reacted in 180 DEG C of baking ovens, you can obtain carbon coating tellurium nano-cable dispersion liquid；
(3) preparation of metal cobalt molybdate and carbon composite nano-fiber：To 350mL carbon coatings tellurium nano-cable obtained above
20mmol sodium molybdates and 20mmol nickel nitrates are sequentially added in dispersion liquid.500mL polytetrafluoroethylene (PTFE) is transferred to after stirring
In reactor, reacted in 180 DEG C of baking ovens after 12h, product is centrifuged, washed, dried in 60 DEG C of vacuum drying chambers
12h, you can obtain dry nickel molybdate and carbon composite nano-fiber.
Obtained composite nano fiber is subjected to transmission electron microscope analysis, as a result referring to Fig. 7.It can be seen that the nickel molybdate and carbon
Composite nano fiber and embodiment 1~4 in cobalt molybdate and carbon composite nano fiber without significant difference, size uniformity, diameter
About 180nm, surface is smooth without any particle, and middle tellurium nano-wire template is still clear.
Embodiment 6
The cobalt molybdate and the composite nano fiber of carbon that embodiment 1 is prepared carry out 500 DEG C of annealings in tube furnace
2h, protective gas is argon gas.
Obtained product is characterized, as a result referring to Fig. 8 and Fig. 9.It can be seen that largely from Fig. 8 transmission electron microscope picture
Nano particle it is high-visible, and be evenly distributed on nanofiber, particle size is about 5nm.Fig. 9 XRD data analyses
It has been shown that, is consistent with the standard card of cobalt molybdate, it was demonstrated that the nano particle is crystalline cobalt molybdate.
Embodiment 7
The cobalt molybdate and the composite nano fiber of carbon that embodiment 1 is prepared carry out 900 DEG C of annealings in tube furnace
2h, protective gas is argon gas.
Obtained product is characterized, as a result referring to Figure 10 and Figure 11.It can be seen that greatly from Figure 10 transmission electron microscope picture
The nano particle of amount is distributed on nanofiber, and particle size is about 20~40nm.Figure 11 XRD data analyses show, with
Simple substance cobalt is consistent with the standard card of molybdenum carbide, it was demonstrated that the nano particle is the mixture phase of crystalline cobalt and molybdenum carbide.
Embodiment 8
The cobalt and molybdenum carbide composite nanometer particle that embodiment 7 is prepared are supported on as elctro-catalyst on carbon fiber,
Method as described above is carrying out the detection of electrochemical electrolysis water H2-producing capacity to it, can by Figure 12 as a result referring to Figure 12
To find out, the mixed catalyst has preferable electro-catalysis to produce the performance of hydrogen under alkaline electrolyte, and it reaches 10mA/cm2With
20mA/cm2Current density need only to 320mV and 365mV overpotential, be preferable numerical value in current document report.
As seen from the above embodiment, the present invention prepares metal molybdate and the method for carbon composite nano-fiber is simple, product
Purity is high, and cost is relatively low, it is easy to large-scale promotion, while the obtained cobalt that is carbonized has excellent with carbonization molybdenum composite material
The catalytic performance of electrochemical electrolysis water hydrogen, has a good application prospect.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. a kind of preparation method of metal molybdate/carbon composite nano-fiber, it is characterised in that comprise the following steps：
A) tellurium nano-wire is mixed with glucose, hydrothermal carbonization reaction is carried out, obtains carbon coating tellurium nano-cable；
B) carbon coating tellurium nano-cable is mixed with metal molybdate presoma, hydrothermal carbonization reaction is carried out, obtains metal molybdic acid
Salt/carbon composite nano-fiber.
2. preparation method according to claim 1, it is characterised in that the tellurium nano-wire is prepared in accordance with the following methods：
Sodium tellurite, polyvinylpyrrolidone, hydrazine hydrate, ammoniacal liquor are mixed in water, hydro-thermal reaction is carried out, obtains tellurium nano-wire
Dispersion liquid；
The tellurium nano-wire dispersion liquid is centrifuged in organic solvent, tellurium nano-wire is obtained.
3. preparation method according to claim 1, it is characterised in that the step A) in, the temperature of hydrothermal carbonization reaction
For 160~200 DEG C, the reaction time is 3~8h.
4. preparation method according to claim 1, it is characterised in that the metal molybdate presoma is sodium molybdate and nitre
Hydrochlorate.
5. preparation method according to claim 4, it is characterised in that the nitrate is cobalt nitrate, nickel nitrate and nitric acid
One or more in manganese.
6. preparation method according to claim 1, it is characterised in that the step B) in, the temperature of hydrothermal carbonization reaction
For 160~200 DEG C, the reaction time is 8~48h.
7. the metal molybdate that the preparation method described in a kind of any one of claim 1~6 is prepared/carbon composite nano is fine
Dimension.
8. a kind of composite of nano-fibre supported particle, it is characterised in that by the system described in any one of claim 1~6
Metal molybdate/carbon composite nano described in metal molybdate/carbon composite nano-fiber or claim 7 prepared by Preparation Method is fine
Dimension is obtained through calcining.
9. the composite of nano-fibre supported particle according to claim 8, it is characterised in that the temperature of the calcining
For 300 DEG C~1200 DEG C.
10. the composite of the nano-fibre supported particle described in any one of claim 8~9 is produced as catalyst in electrochemistry
The application in hydrogen field.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194440A (en) * | 2019-03-27 | 2019-09-03 | 吉林建筑大学 | A kind of method that hydrothermal synthesis prepares simple substance tellurium |
| CN111333051A (en) * | 2020-01-10 | 2020-06-26 | 厦门理工学院 | Composite material taking starch as carbon-based load, preparation method and application thereof |
| CN112110497A (en) * | 2020-09-28 | 2020-12-22 | 中国科学技术大学 | Lanthanide metal-doped lanthanum cobaltate type nanotube material, preparation method thereof and method for producing hydrogen by electrolyzing water |
| CN113058660A (en) * | 2021-03-31 | 2021-07-02 | 扬州大学 | Catalyst carrier and preparation method thereof, catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090009419A (en) * | 2007-07-20 | 2009-01-23 | (주)바이오니아 | A method for preparing nanocomposites consisting of carbon nanostructures and metal |
| CN101367521A (en) * | 2008-10-13 | 2009-02-18 | 复旦大学 | Synthesis of stephanoporate molybdenum carbide nano-wire |
| CN103285920A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Three-dimensional fiber-based aerogel catalyst carrier and preparation method thereof |
| CN104386753A (en) * | 2014-11-21 | 2015-03-04 | 合肥工业大学 | Method for preparing molybdenum disulfide nanotube |
| CN105642326A (en) * | 2016-01-28 | 2016-06-08 | 中国科学技术大学 | Porous-carbon loaded metal composite material and preparing method and application thereof |
| CN105887132A (en) * | 2016-06-24 | 2016-08-24 | 复旦大学 | Molybdenum diselenide nanosheet/carbon nanofiber hybrid material and preparation method thereof |
-
2017
- 2017-04-10 CN CN201710228674.0A patent/CN106964362A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090009419A (en) * | 2007-07-20 | 2009-01-23 | (주)바이오니아 | A method for preparing nanocomposites consisting of carbon nanostructures and metal |
| CN101367521A (en) * | 2008-10-13 | 2009-02-18 | 复旦大学 | Synthesis of stephanoporate molybdenum carbide nano-wire |
| CN103285920A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Three-dimensional fiber-based aerogel catalyst carrier and preparation method thereof |
| CN104386753A (en) * | 2014-11-21 | 2015-03-04 | 合肥工业大学 | Method for preparing molybdenum disulfide nanotube |
| CN105642326A (en) * | 2016-01-28 | 2016-06-08 | 中国科学技术大学 | Porous-carbon loaded metal composite material and preparing method and application thereof |
| CN105887132A (en) * | 2016-06-24 | 2016-08-24 | 复旦大学 | Molybdenum diselenide nanosheet/carbon nanofiber hybrid material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAI-SHENG QIAN，ET AL: "Synthesis of Uniform Te@Carbon-Rich Composite Nanocables with Photoluminescence Properties and Carbonaceous Nanofibers by the Hydrothermal Carbonization of Glucose", 《CHEM. MATER.》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194440A (en) * | 2019-03-27 | 2019-09-03 | 吉林建筑大学 | A kind of method that hydrothermal synthesis prepares simple substance tellurium |
| CN111333051A (en) * | 2020-01-10 | 2020-06-26 | 厦门理工学院 | Composite material taking starch as carbon-based load, preparation method and application thereof |
| CN111333051B (en) * | 2020-01-10 | 2021-05-28 | 厦门理工学院 | Composite material taking starch as carbon-based load, preparation method and application thereof |
| CN112110497A (en) * | 2020-09-28 | 2020-12-22 | 中国科学技术大学 | Lanthanide metal-doped lanthanum cobaltate type nanotube material, preparation method thereof and method for producing hydrogen by electrolyzing water |
| CN112110497B (en) * | 2020-09-28 | 2022-04-19 | 中国科学技术大学 | Lanthanide metal-doped lanthanum cobaltate type nanotube material, preparation method thereof and method for producing hydrogen by electrolyzing water |
| CN113058660A (en) * | 2021-03-31 | 2021-07-02 | 扬州大学 | Catalyst carrier and preparation method thereof, catalyst and preparation method and application thereof |
| CN113058660B (en) * | 2021-03-31 | 2023-10-27 | 扬州大学 | Catalyst carrier and preparation method thereof, catalyst and preparation method and application thereof |
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