CN110270362A - A kind of nitrogen co-doped carbide nanorods of manganese and its preparation method and application - Google Patents
A kind of nitrogen co-doped carbide nanorods of manganese and its preparation method and application Download PDFInfo
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- CN110270362A CN110270362A CN201910597196.XA CN201910597196A CN110270362A CN 110270362 A CN110270362 A CN 110270362A CN 201910597196 A CN201910597196 A CN 201910597196A CN 110270362 A CN110270362 A CN 110270362A
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- manganese
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- molybdenum
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000011572 manganese Substances 0.000 title claims abstract description 79
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 69
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000002073 nanorod Substances 0.000 title claims abstract description 42
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 27
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 14
- -1 modified molybdenum amine Chemical class 0.000 claims abstract description 13
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical group N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 16
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 12
- 229910039444 MoC Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 235000016768 molybdenum Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 229910018337 Mn(C2 H3 O2)2 Inorganic materials 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910003178 Mo2C Inorganic materials 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 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
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-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
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
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- 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 present invention relates to a kind of preparation methods of the nitrogen co-doped carbide nanorods of manganese, include the following steps: S1, molybdenum source, manganese salt and aniline are added to the water and are ultrasonically formed mixing turbid, wherein, the molar ratio of manganese atom and molybdenum atom is 0.001-0.5: 1, and the molar ratio of aniline and molybdenum atom is 1-10: 1；S2, by the way that the pH to 3-6 of inorganic acid regulation mixing turbid is added, reaction obtains the modified molybdenum amine presoma of manganese；S3 calcines the modified molybdenum amine presoma of manganese in the calcination atmosphere of reproducibility and obtains the nitrogen co-doped carbide nanorods of manganese.The present invention also provides the nitrogen co-doped carbide nanorods of the manganese obtained by above-mentioned preparation method and its as the application of elctro-catalyst.The preparation method of the nitrogen co-doped carbide nanorods of manganese according to the present invention, process is simple, yield is high, at low cost and be easy to be mass produced.
Description
Technical field
The present invention relates to electro-catalysis hydrogen manufacturing, relate more specifically to a kind of nitrogen co-doped carbide nanorods of manganese and its preparation
Methods and applications.
Background technique
Electric energy hydrogen production by water decomposition with booming renewable energy (such as solar energy, wind energy) conversion is to realize greatly
Scale prepares the important method of high-purity hydrogen.Water electrolysis hydrogen production catalyst currently used in the market is platinum based noble metal catalysis
Agent, H2-producing capacity is prominent, but there is also the problems such as at high price, reserves are limited simultaneously.Therefore, cheap, source is explored
Abundant, efficient base metal catalyst for preparing hydrogen has important practical significance.
Molybdenum carbide is as a kind of transition metal carbide, because of its eka-platinium electronic structure, high chemical stability and outstanding
Catalytic performance and attract attention.But molybdenum carbide generally existing particle agglomeration, surface contamination carbon covering etc. during the preparation process
Problem.Simultaneously as the d track density that molybdenum atom does not occupy in molybdenum carbide is larger, lead to catalyst-hydrogen adsorption energy (Δ GH*)
It is excessive, it is unfavorable for the desorption of hydrogen, liberation of hydrogen dynamics is slow.
Summary of the invention
In order to solve particle agglomeration existing for carbide nanorods in the prior art, carbon is polluted in surface covering and unfavorable
In hydrogen is desorbed the problems such as, the present invention provides a kind of nitrogen co-doped carbide nanorods of manganese and its preparation method and application.
The present invention provides a kind of preparation method of nitrogen co-doped carbide nanorods of manganese, includes the following steps: S1, by molybdenum
Source, manganese salt and aniline, which are added to the water, is ultrasonically formed mixing turbid, wherein the molar ratio of manganese atom and molybdenum atom is 0.001-0.5
: 1, the molar ratio of aniline and molybdenum atom is 1-10: 1；S2, by the way that the pH to 3-6 of inorganic acid regulation mixing turbid, reaction is added
Obtain modified molybdenum amine presoma (the also known as MoO of manganesexAmine hybrid inorganic-organic presoma)；S3, in the calcining gas of reproducibility
The modified molybdenum amine presoma of manganese is calcined in atmosphere obtains the nitrogen co-doped carbide nanorods of manganese.
The present invention optimizes molybdenum carbide electronic structure by manganese nitrogen codope, reduces catalyst-hydrogen adsorption energy, adds
Fast molybdenum carbide liberation of hydrogen dynamics improves electrolysis water hydrogen evolution activity.Specifically, presoma is made with the modified molybdenum amine of manganese, regulates and controls forerunner
The element proportion of Mn, Mo in body ingredient, calcining obtains the nitrogen co-doped carbide nanorods elctro-catalyst of manganese in a reducing atmosphere.
The nitrogen co-doped carbide nanorods of the manganese that preparation method according to the present invention obtains are in Raman spectrum, high power transmission electron microscope photo
In, carbon-free characteristic peak, lattice fringe show its surface without pollution carbon；Inductively coupled plasma body emits light simultaneously
The presence of the proof such as spectrum, x-ray photoelectron spectroscopy Mn, N element.In short, preparation method according to the present invention process is simple, warp
Ji is reasonable, it is easy to accomplish large-scale production.
Preferably, in the step S1, molybdenum source and manganese salt ultrasound is soluble in water, aniline is added as carbon source.
Preferably, the molar concentration of the molybdenum atom in the mixing turbid is 0.1-1.0mol/L.In preferred embodiment
In, the molar concentration of the molybdenum atom in the mixing turbid is 0.3-1mol/L.
Preferably, the molar ratio of the manganese atom and molybdenum atom is 0.01-0.5: 1.
Preferably, the molar ratio of the aniline and molybdenum atom is 2.4-10: 1.
Preferably, the molybdenum source is selected from ammonium heptamolybdate ((NH4)6Mo7O24·4H2O), in sodium molybdate and potassium molybdate at least
It is a kind of.
Preferably, the manganese salt is selected from least one of manganese acetate, manganese nitrate and manganese chloride.
Preferably, in the step S2, inorganic acid for adjusting pH is added dropwise to there is yellow mercury oxide, reacts 2- at 40-80 DEG C
12 hours, through suction filtration, washing, drying, obtain the modified molybdenum amine presoma of manganese.In a preferred embodiment, reactant is in water-bath
It is reacted in pot, filters product and sufficiently washed with ethyl alcohol.In a preferred embodiment, 4 are stirred to react at 60 DEG C
Hour.
Preferably, the inorganic acid is selected from least one of dilute hydrochloric acid, dilute sulfuric acid and dust technology.Preferred real
It applies in example, inorganic acid is dilute hydrochloric acid, dilute sulfuric acid or the dust technology etc. that concentration is 0.1-3M.In a preferred embodiment,
The inorganic acid is 1M HCl solution.
Preferably, the pH to 4-5 of turbid is mixed by the way that inorganic acid regulation is added.
Preferably, in the step S3, it is calcined in tube furnace, calcined product acid bubble, centrifugation is washed
It is dry after to neutrality, obtain the nitrogen co-doped carbide nanorods of manganese.
Preferably, acid used in the acid bubble is selected from least one of hydrochloric acid and sulfuric acid.In a preferred implementation
In example, the sour H for being 0.5M used in the acid bubble2SO4Solution.
Preferably, in the step S3,600-800 DEG C of calcination temperature is risen to the heating rate of 2-10 DEG C/min
Lower calcining 2-10 hours.In a preferred embodiment, which is 650-750 DEG C.In a preferred embodiment,
The calcination temperature is 700 DEG C.
Preferably, the calcination atmosphere is the mixed gas of inert gas and hydrogen.In a preferred embodiment, described
The volume content of hydrogen in calcination atmosphere is 0.05-0.25.In a preferred embodiment, the calcination atmosphere is H2And Ar
Mixed atmosphere.
The present invention also provides the nitrogen co-doped carbide nanorods of the manganese obtained by above-mentioned preparation method.
Preferably, the nitrogen co-doped carbide nanorods of the manganese are accumulated by the molybdenum carbide nano particle of particle size uniformity
It forms.Particularly, the nitrogen co-doped carbide nanorods of the manganese have pore structure abundant, be conducive to electrolyte infiltration and
The spilling of hydrogen.
Application the present invention also provides the nitrogen co-doped carbide nanorods of above-mentioned manganese as elctro-catalyst.
Preferably, the nitrogen co-doped carbide nanorods of the manganese are used for water electrolysis hydrogen production.
Preferably, the nitrogen co-doped carbide nanorods of the manganese are used as the electrolysis water liberation of hydrogen catalyst under acid medium.?
In preferred embodiment, in 0.5M H2SO4In solution, in 20mA/cm2Overpotential under current density is 192-226mV (phase
To reversible hydrogen electrode), Tafel slope 66-103mV/dec, and continuous operation still keeps good stability for 24 hours.
The preparation method of the nitrogen co-doped carbide nanorods of manganese according to the present invention, process is simple, yield is high, it is at low cost,
And it is easy to be mass produced.Specifically, the present invention obtains the modified molybdenum amine presoma of manganese using the method for hybrid inorganic-organic,
Then calcining obtains the nitrogen co-doped carbide nanorods of manganese in a reducing atmosphere, and this preparation method by presoma can have
Effect, which is reduced, reunites.Moreover, the nitrogen co-doped carbide nanorods of manganese of the invention pass through doping valence electron (d5) abundant and electronegativity
Small manganese element regulates and controls the electronic structure of molybdenum carbide, and accelerated carbonation molybdenum liberation of hydrogen dynamics improves electrolysis water hydrogen evolution activity.Separately
Outside, according to the detection peak D typical less than carbon and the peak G in Raman spectrum it is found that the nitrogen co-doped molybdenum carbide of manganese provided by the invention
The problem of nanometer rods pollute carbon there is no surface covering, catalytic site can sufficiently be exposed, to obtain without precious metal
High-activity electrolytic elutriation hydrogen catalyst shows good electrolysis water hydrogen evolution activity and stability in acid medium.
Detailed description of the invention
Fig. 1 is the XRD diagram of the nitrogen co-doped carbide nanorods of manganese of different manganese molybdenum proportion preparations；
Fig. 2 is the XRD diagram of sample A and sample B；
Fig. 3 is the SEM figure (a) and high power TEM figure (b) of the nitrogen co-doped carbide nanorods of manganese prepared by embodiment 1；
Fig. 4 is the Raman characterization of the nitrogen co-doped carbide nanorods of manganese of different manganese molybdenum proportion preparations；
Fig. 5 is the full stave sign of XPS of the nitrogen co-doped carbide nanorods of manganese prepared by embodiment 1；
Fig. 6 is the water electrolysis hydrogen production catalytic performance table of the nitrogen co-doped carbide nanorods of manganese of different manganese molybdenum proportion preparations
Sign；
Fig. 7 is the stability characterization of the water electrolysis hydrogen production of the nitrogen co-doped carbide nanorods of manganese prepared by embodiment 1.
Specific embodiment
With reference to the accompanying drawing, presently preferred embodiments of the present invention is provided, and is described in detail.
Embodiment 1
Weigh carbon source aniline 1.25g, ammonium heptamolybdate ((NH4)6Mo7O24·4H2O) 1g and manganese acetate (Mn
(C2H3O2)2·4H2O) 13.8mg (molar concentration of molybdenum atom is 0.3mol/L, and the molar ratio of aniline and molybdenum atom is 2.4: 1,
0.01) in beaker, to add water 20mL, ultrasonic disperse is added 1M HCl solution and adjusts pH to 4-5,60 Mn: Mo molar ratio
After DEG C stirred in water bath 4h, yellow product is filtered and is separated, it is dry.By the product after drying in 10%H2It is calcined under/Ar atmosphere
To 700 DEG C, 3h is kept the temperature, then by the H of calcined product 0.5M2SO4Solution steeps for 24 hours, removes unstable in catalyst
Species, dry after finally centrifugation is washed to neutrality, resulting product is denoted as Mn, N-Mo2C-0.01。
The electro-chemical test of the nitrogen co-doped carbide nanorods water electrolysis hydrogen production of manganese sequentially includes the following steps:
Firstly, weighing the above-mentioned product of 4mg and 0.5mg carbon black dispersion in 2ml isopropanol and 60uLNafion solution (5%)
Mixed solution in, ultrasound obtain evenly dispersed suspension, then take the above-mentioned hanging drop of 80uL to diameter for 6mm wave
On carbon electrode, working electrode can be obtained after natural drying；Then water electrolysis hydrogen production performance test is in electrochemical workstation
(CHI760E, Shanghai Chen Hua) carries out, using three-electrode system, with 0.5M H2SO4Solution is electrolyte, and graphite rod is to electricity
Pole, the Ag/AgCl electrode of 3M KCl solution filling are reference electrode, and the speed of sweeping of linear sweep voltammetry curve is 5mV/s, experiment
Data do not carry out IR correction, and electrode potential is relative to reversible hydrogen electrode (RHE), and conversion method is as follows: ERHE=EAg/AgCl+
0.059*pH+0.209。
Embodiment 2
Preparation process and step and above-described embodiment 1 in embodiment 2 is essentially identical, unlike: weigh manganese acetate
(Mn(C2H3O2)2·4H2O quality) is 1.4mg (Mn:Mo molar ratio is 0.001), and catalyst obtained is denoted as Mn, N-
Mo2C-0.001.The water electrolysis hydrogen production catalytic performance characterization of catalyst is same
Embodiment 1.
Embodiment 3
Preparation process and step and above-described embodiment 1 in embodiment 3 is essentially identical, unlike: weigh manganese acetate
(Mn(C2H3O2)2·4H2O quality) is 7.0mg (Mn: Mo molar ratio is 0.005), and catalyst obtained is denoted as Mn, N-
Mo2C-0.005.The water electrolysis hydrogen production catalytic performance characterization of catalyst is same
Embodiment 1.
Embodiment 4
Preparation process and step and above-described embodiment 1 in embodiment 4 is essentially identical, unlike: weigh manganese acetate
(Mn(C2H3O2)2·4H2O quality) is 69.4mg (Mn: Mo molar ratio is 0.05), and catalyst obtained is denoted as Mn, N-
Mo2C-0.05.The water electrolysis hydrogen production catalytic performance of catalyst is characterized with embodiment 1.
Embodiment 5
Preparation process and step and above-described embodiment 1 in embodiment 5 is essentially identical, unlike: acetic acid is not added
Manganese (Mn (C2H3O2)2·4H2O), catalyst obtained is denoted as Mn, N-Mo2C-0.The water electrolysis hydrogen production catalytic performance table of catalyst
Sign is the same as embodiment 1.
Embodiment 6
Preparation process and step and above-described embodiment 1 in embodiment 6 is essentially identical, unlike: aniline and molybdenum atom
Molar ratio be 10: 1, the molar concentration of molybdenum atom is 1.0mol/L, and Mn: Mo molar ratio is 0.5.The sample is labeled as sample
A。
Embodiment 7
Preparation process and step and above-described embodiment 1 in embodiment 7 is essentially identical, unlike: aniline and molybdenum atom
Molar ratio be 1:1, the molar concentration of molybdenum atom is 0.3mol/L, and Mn: Mo molar ratio is 0.05.The sample is labeled as sample
B。
The following table 1 is the ICP-OES knot of the manganese content of the nitrogen co-doped carbide nanorods of manganese of different manganese molybdenums proportion preparation
Fruit shows that manganese is successfully incorporated into molybdenum carbide crystal.
Table 1
Fig. 1 is the XRD diagram of the nitrogen co-doped carbide nanorods of manganese of different manganese molybdenums proportion preparation, can from Fig. 1
Out, the catalyst of preparation is β-Mo2C, and the additive Mn of certain content range will not have an impact to crystalline component.
Fig. 2 is the XRD diagram of sample A and sample B.From figure 2 it can be seen that sample A and sample B are β-Mo2C。
Fig. 3 is that the SEM of the nitrogen co-doped carbide nanorods of manganese prepared by embodiment 1 schemes (a) and high power TEM schemes (b), this
Kind carbide nanorods are accumulated by the molybdenum carbide nano particle of particle size uniformity, have pore structure abundant, and high power
There is no the lattice fringe of carbon under transmission electron microscope.
Fig. 4 is the Raman characterization of the nitrogen co-doped carbide nanorods of manganese of different manganese molybdenums proportion preparation, in Raman map only
There is the characteristic peak of molybdenum carbide, carbon-free characteristic peak (peak D, the peak G) shows that the not contaminated carbon of the catalyst surface of preparation covers
Lid.
Fig. 5 is the full stave sign of XPS of the nitrogen co-doped carbide nanorods of manganese prepared by embodiment 1, the nitrogen signal in full spectrum
Show in nitrogen incorporation molybdenum carbide crystal.
Fig. 6 is the water electrolysis hydrogen production catalytic performance table of the nitrogen co-doped carbide nanorods of manganese of different manganese molybdenums proportion preparation
Sign, (a) are linear sweep voltammetry curve, (b) are Tafel curve.Work as current density from can be seen that in (a) for 20mA/
cm2, Mn, N-Mo2C-0、Mn、N-Mo2C-0.001、Mn、 N-Mo2C-0.005、Mn、N-Mo2C-0.01、Mn、N-Mo2C-0.05
Required overpotential is respectively 226mV, 208mV, 195mV, 192mV, 218mV, this shows Mn, N-Mo2The electricity of C-0.01
The catalytic performance for solving water hydrogen manufacturing is best.From in (b) as can be seen that Mn, N-Mo2C-0、Mn、 N-Mo2C-0.001、Mn、N-Mo2C-
0.005、Mn、N-Mo2C-0.01、Mn、N-Mo2The Tafel slope of C-0.05 is respectively 103mV/dec, 72mV/dec, 70mV/
Dec, 66mV/dec, 88mV/dec show that their rate-limiting step is all Volmer-Heyrovsky step, wherein
Volmer-Heyrovsky step is the adsorption-desorption step of Hydrogen Proton, according to Tafel slope during water electrolysis hydrogen production
The rate-limiting step of available reaction, Tafel slope are the smaller the better.
Fig. 7 is that the stability of the water electrolysis hydrogen production of the nitrogen co-doped carbide nanorods of manganese prepared by embodiment 1 characterizes (i-t
Curve), after operation for 24 hours, current density stills remain in 7.2mA/cm2Left and right, shows its good stability.
Above-described, only presently preferred embodiments of the present invention, the range being not intended to limit the invention are of the invention
Above-described embodiment can also make a variety of changes.I.e. all claims applied according to the present invention and description institute
Simple, the equivalent changes and modifications made, fall within the claims of the invention patent.The not detailed description of the present invention
Be routine techniques content.
Claims (10)
1. a kind of preparation method of the nitrogen co-doped carbide nanorods of manganese, which comprises the steps of:
Molybdenum source, manganese salt and aniline are added to the water and are ultrasonically formed mixing turbid by S1, wherein the molar ratio of manganese atom and molybdenum atom
It is 0.001-0.5: 1, the molar ratio of aniline and molybdenum atom is 1-10: 1；
S2, by the way that the pH to 3-6 of inorganic acid regulation mixing turbid is added, reaction obtains the modified molybdenum amine presoma of manganese；
S3 calcines the modified molybdenum amine presoma of manganese in the calcination atmosphere of reproducibility and obtains the nitrogen co-doped carbide nanorods of manganese.
2. preparation method according to claim 1, which is characterized in that the molar concentration of the molybdenum atom in the mixing turbid
For 0.1-1.0mol/L.
3. preparation method according to claim 1, which is characterized in that the molybdenum source is selected from ammonium heptamolybdate, sodium molybdate and molybdenum
At least one of sour potassium.
4. preparation method according to claim 1, which is characterized in that the manganese salt is selected from manganese acetate, manganese nitrate and chlorination
At least one of manganese.
5. preparation method according to claim 1, which is characterized in that the inorganic acid be selected from dilute hydrochloric acid, dilute sulfuric acid and
At least one of dust technology.
6. preparation method according to claim 1, which is characterized in that in the step S3, with the liter of 2-10 DEG C/min
Warm rate rises under 600-800 DEG C of calcination temperature and calcines 2-10 hours.
7. preparation method according to claim 1, which is characterized in that the calcination atmosphere is the mixed of inert gas and hydrogen
Close gas.
8. preparation method according to claim 7, which is characterized in that the volume content of the hydrogen in the calcination atmosphere is
0.05-0.25。
9. a kind of nitrogen co-doped carbide nanorods of the manganese that preparation method according to claim 1 to 8 obtains.
10. a kind of application of nitrogen co-doped carbide nanorods of manganese according to claim 9 as elctro-catalyst.
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