CN110270362B - Manganese-nitrogen co-doped molybdenum carbide nanorod and preparation method and application thereof - Google Patents
Manganese-nitrogen co-doped molybdenum carbide nanorod and preparation method and application thereof Download PDFInfo
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- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 54
- 239000002073 nanorod Substances 0.000 title claims abstract description 43
- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 21
- -1 manganese-modified molybdenum amine Chemical class 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 4
- 230000002829 reductive effect Effects 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 37
- 239000011572 manganese Substances 0.000 claims description 35
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 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 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound 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
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 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
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 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
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 description 37
- 229910052739 hydrogen Inorganic materials 0.000 description 37
- 239000003054 catalyst Substances 0.000 description 17
- 238000005868 electrolysis reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 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
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000002378 acidificating effect Effects 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
- 239000006229 carbon black Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000000203 mixture Substances 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
- 238000001878 scanning electron micrograph Methods 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
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 239000004615 ingredient Substances 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
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- 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
Abstract
The invention relates to a preparation method of a manganese-nitrogen co-doped molybdenum carbide nanorod, which comprises the following steps: s1, adding a molybdenum source, manganese salt and aniline into water, and performing ultrasonic treatment to form a mixed turbid liquid, wherein the molar ratio of manganese atoms to molybdenum atoms is 0.001-0.5:1, and the molar ratio of aniline to molybdenum atoms is 1-10: 1; s2, regulating the pH value of the mixed turbid liquid to 3-6 by adding inorganic acid, and reacting to obtain a manganese-modified molybdenum amine precursor; and S3, calcining the manganese-modified molybdenum amine precursor in a reductive calcining atmosphere to obtain the manganese-nitrogen co-doped molybdenum carbide nanorod. The invention also provides the manganese-nitrogen co-doped molybdenum carbide nanorod obtained by the preparation method and application thereof as an electrocatalyst. The preparation method of the manganese-nitrogen co-doped molybdenum carbide nanorod has the advantages of simple process, high yield, low cost and easiness in large-scale production.
Description
Technical Field
The invention relates to electrocatalytic hydrogen production, in particular to a manganese-nitrogen co-doped molybdenum carbide nanorod and a preparation method and application thereof.
Background
The hydrogen production by water decomposition with the electric energy converted from the vigorously developed renewable energy sources (such as solar energy, wind energy and the like) is an important method for realizing the large-scale preparation of high-purity hydrogen. The catalyst for hydrogen production by water electrolysis used in the current market is a platinum-based noble metal catalyst, has outstanding hydrogen production performance, but also has the problems of high price, limited reserves and the like. Therefore, the exploration of the non-noble metal hydrogen production catalyst which is low in price, rich in source and high in efficiency has important practical significance.
Molybdenum carbide is a transition metal carbide that has received attention for its platinum-like electronic structure, high chemical stability, and outstanding catalytic properties. However, the problems of particle agglomeration, surface pollution carbon coverage and the like generally exist in the preparation process of molybdenum carbide. Meanwhile, the density of the d orbitals not occupied by molybdenum atoms in molybdenum carbide is high, so that the catalyst-hydrogen adsorption energy (delta G) is causedH*) Too large and disadvantageousThe desorption of hydrogen is slow in kinetics of hydrogen evolution.
Disclosure of Invention
In order to solve the problems of particle agglomeration, surface covering of polluted carbon, inconvenience in hydrogen desorption and the like of the molybdenum carbide nanorod in the prior art, the invention provides a manganese-nitrogen co-doped molybdenum carbide nanorod and a preparation method and application thereof.
The invention provides a preparation method of a manganese-nitrogen co-doped molybdenum carbide nanorod, which comprises the following steps: s1, adding a molybdenum source, manganese salt and aniline into water, and performing ultrasonic treatment to form a mixed turbid liquid, wherein the molar ratio of manganese atoms to molybdenum atoms is 0.001-0.5:1, and the molar ratio of aniline to molybdenum atoms is 1-10: 1; s2, regulating the pH of the mixed turbid liquid to 3-6 by adding inorganic acid, and reacting to obtain a manganese-modified molybdenum amine precursor (also called MoO)xAmine organic-inorganic hybrid precursors); and S3, calcining the manganese-modified molybdenum amine precursor in a reductive calcining atmosphere to obtain the manganese-nitrogen co-doped molybdenum carbide nanorod.
According to the invention, the electronic structure of molybdenum carbide is optimized through manganese and nitrogen co-doping, the catalyst-hydrogen adsorption energy is reduced, the dynamics of molybdenum carbide hydrogen evolution is accelerated, and the activity of electrolytic water hydrogen evolution is improved. Specifically, manganese modified molybdenum amine is used as a precursor, the element proportion of Mn and Mo in the precursor ingredients is regulated and controlled, and the manganese nitrogen co-doped molybdenum carbide nanorod electrocatalyst is obtained by calcining in a reducing atmosphere. The manganese-nitrogen co-doped molybdenum carbide nanorod obtained by the preparation method does not contain carbon characteristic peaks and lattice stripes in Raman spectra and high-power transmission electron microscope photos, and the surface of the nanorod does not contain polluted carbon; meanwhile, the existence of Mn and N elements is proved by inductively coupled plasma emission spectrum, X-ray photoelectron spectrum and the like. In a word, the preparation method has simple flow, is economic and reasonable, and is easy to realize large-scale production.
Preferably, in the step S1, the molybdenum source and the manganese salt are ultrasonically dissolved in water, and aniline is added as the carbon source.
Preferably, the molar concentration of the molybdenum atoms in the mixed turbid liquid is 0.1-1.0 mol/L. In a preferred embodiment, the molar concentration of molybdenum atoms in the mixed turbid liquid is 0.3-1 mol/L.
Preferably, the molar ratio of manganese atoms to molybdenum atoms is 0.01-0.5: 1.
Preferably, the molar ratio of aniline to molybdenum atoms is 2.4-10: 1.
Preferably, the molybdenum source is selected from ammonium heptamolybdate ((NH)4)6Mo7O24·4H2O), sodium molybdate, and potassium molybdate.
Preferably, the manganese salt is selected from at least one of manganese acetate, manganese nitrate and manganese chloride.
Preferably, in the step S2, inorganic acid is added dropwise to adjust the pH until yellow precipitate appears, the reaction is performed at 40-80 ℃ for 2-12 hours, and the manganese-modified molybdenum amine precursor is obtained after suction filtration, washing and drying. In a preferred embodiment, the reactants are reacted in a water bath and the product is filtered and washed thoroughly with ethanol. In a preferred embodiment, the reaction is stirred for 4 hours at 60 ℃.
Preferably, the inorganic acid is at least one selected from the group consisting of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid. In a preferred embodiment, the inorganic acid is dilute hydrochloric acid, dilute sulfuric acid, or dilute nitric acid, etc., at a concentration of 0.1 to 3M. In a preferred embodiment, the mineral acid is 1M HCl solution.
Preferably, the pH of the mixed suspension is adjusted to 4 to 5 by adding mineral acid.
Preferably, in the step S3, calcining is performed in a tube furnace, and the calcined product is acid-soaked, centrifugally washed to neutrality, and then dried to obtain the manganese-nitrogen co-doped molybdenum carbide nanorod.
Preferably, the acid used for the acid foam is selected from at least one of hydrochloric acid and sulfuric acid. In a preferred embodiment, the acid used in the acid foam is 0.5M H2SO4And (3) solution.
Preferably, in the step S3, the calcination is performed at a temperature rising rate of 2-10 ℃/min to a calcination temperature of 600-800 ℃ for 2-10 hours. In a preferred embodiment, the calcination temperature is 650-750 ℃. In a preferred embodiment, the calcination temperature is 700 ℃.
Preference is given toThe calcining atmosphere is a mixed gas of inert gas and hydrogen. In a preferred embodiment, the hydrogen is present in the calcination atmosphere in an amount of 0.05 to 0.25 by volume. In a preferred embodiment, the calcination atmosphere is H2And Ar.
The invention also provides the manganese-nitrogen co-doped molybdenum carbide nanorod obtained by the preparation method.
Preferably, the manganese-nitrogen co-doped molybdenum carbide nanorod is formed by stacking molybdenum carbide nanoparticles with uniform particle sizes. Particularly, the manganese-nitrogen co-doped molybdenum carbide nanorod has a rich pore structure, and is favorable for permeation of electrolyte and overflow of hydrogen.
The invention also provides the application of the manganese-nitrogen co-doped molybdenum carbide nanorod as an electrocatalyst.
Preferably, the manganese-nitrogen co-doped molybdenum carbide nanorod is used for hydrogen production through water electrolysis.
Preferably, the manganese-nitrogen co-doped molybdenum carbide nanorod is used as a hydrogen evolution catalyst for water electrolysis in an acidic medium. In the preferred embodiment, at 0.5M H2SO4In solution at 20mA/cm2The overpotential at the current density is 192-226mV (relative to a reversible hydrogen electrode), the Tafel slope is 66-103mV/dec, and good stability is still maintained after continuous operation for 24 hours.
The preparation method of the manganese-nitrogen co-doped molybdenum carbide nanorod has the advantages of simple process, high yield, low cost and easiness in large-scale production. Specifically, the manganese modified molybdenum amine precursor is obtained by an organic-inorganic hybridization method, and then the manganese nitrogen co-doped molybdenum carbide nano rod is obtained by calcining in a reducing atmosphere. Moreover, the manganese-nitrogen co-doped molybdenum carbide nanorod of the invention is doped with valence electrons (d)5) The manganese element with rich and small electronegativity is used for regulating and controlling the electronic structure of the molybdenum carbide, accelerating the dynamics of hydrogen evolution of the molybdenum carbide and improving the activity of hydrogen evolution of electrolyzed water. In addition, according to the fact that the typical D peak and G peak of carbon cannot be detected in the Raman spectrum, the manganese-nitrogen co-doped molybdenum carbide nanorod provided by the invention does not have the problem that the surface is covered with polluted carbon and is catalyzedThe chemical sites can be fully exposed, so that the high-activity hydrogen electrolysis and evolution catalyst without noble metal is obtained, and the high-activity hydrogen electrolysis and evolution catalyst shows good hydrogen electrolysis and evolution activity and stability in an acidic medium.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of manganese-nitrogen-codoped molybdenum carbide nanorods prepared by different manganese-molybdenum ratios;
FIG. 2 is an XRD pattern for sample A and sample B;
FIG. 3 is an SEM image (a) and a high-power TEM image (b) of the manganese-nitrogen co-doped molybdenum carbide nanorods prepared in example 1;
FIG. 4 is a Raman representation of manganese-nitrogen co-doped molybdenum carbide nanorods prepared at different manganese-molybdenum ratios;
FIG. 5 is an XPS survey spectrum of manganese nitrogen co-doped molybdenum carbide nanorods prepared in example 1;
FIG. 6 shows the catalytic performance characterization of the manganese-nitrogen co-doped molybdenum carbide nanorods for hydrogen production by electrolyzing water, prepared according to different manganese-molybdenum ratios;
FIG. 7 is a stability characterization of hydrogen production by water electrolysis of manganese-nitrogen co-doped molybdenum carbide nanorods prepared in example 1.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
Weighing 1.25g of carbon source aniline and ammonium heptamolybdate ((NH)4)6Mo7O24·4H2O)1g, and manganese acetate (Mn (C)2H3O2)2·4H2O)13.8mg (the molar concentration of molybdenum atoms is 0.3mol/L, the molar ratio of aniline to molybdenum atoms is 2.4: 1, and the molar ratio of Mn to Mo is 0.01) is put into a beaker, 20mL of water is added for ultrasonic dispersion, 1M HCl solution is added to adjust the pH value to 4-5, the mixture is stirred in a water bath at the temperature of 60 ℃ for 4 hours, and then a yellow product is filtered, separated and dried. The dried product was washed with 10% H2Calcining under Ar atmosphere to 700 deg.C, keeping the temperature for 3H, and then using 0.5M H to calcine the product2SO4Soaking the solution for 24h, removing unstable species in the catalyst, finally centrifugally washing the solution to be neutral, and drying the solution to obtain the productMn， N-Mo2C-0.01。
The electrochemical test of hydrogen production by electrolyzing water by using the manganese-nitrogen co-doped molybdenum carbide nanorod is carried out according to the following steps:
firstly, weighing 4mg of the product and 0.5mg of carbon black, dispersing the product and the carbon black in a mixed solution of 2ml of isopropanol and 60uL of a liquid (5%), performing ultrasonic treatment to obtain a uniformly dispersed suspension, then dropping 80uL of the suspension onto a wavy carbon electrode with the diameter of 6mm, and naturally drying to obtain a working electrode; then the performance test of hydrogen production by water electrolysis is carried out in an electrochemical workstation (CHI760E, Shanghai Chenghua) by adopting a three-electrode system and adopting a 0.5M H2SO4The solution is electrolyte, the graphite rod is counter electrode, the Ag/AgCl electrode filled with 3M KCl solution is reference electrode, the sweep rate of linear sweep voltammetry is 5mV/s, the experimental data is not corrected by IR, the electrode potential is relative to the Reversible Hydrogen Electrode (RHE), and the conversion method is as follows: eRHE＝EAg/AgCl+0.059*pH+0.209。
Example 2
The procedure and procedure for the preparation of example 2 are essentially the same as in example 1 above, except that: weighing manganese acetate (Mn (C)2H3O2)2·4H2O) was 1.4mg (Mn: mo molar ratio of 0.001), the catalyst obtained is noted as Mn, N-Mo2C-0.001. The catalytic performance of the catalyst for producing hydrogen by electrolyzing water is characterized by the same
Example 1.
Example 3
The procedure and procedure for the preparation of example 3 are essentially the same as in example 1 above, except that: weighing manganese acetate (Mn (C)2H3O2)2·4H2O) in a mass of 7.0mg (Mn: Mo molar ratio of 0.005) and the catalyst obtained is noted Mn, N-Mo2C-0.005. The catalytic performance of the catalyst for producing hydrogen by electrolyzing water is characterized by the same
Example 1.
Example 4
The procedure and procedure for the preparation of example 4 are essentially the same as in example 1 above, except that: weighing manganese acetate (Mn (C)2H3O2)2·4H2O) in an amount of 69.4mg (Mn: Mo molar ratio of 0.05) was added to the solution, and the catalyst obtained was designated Mn, N-Mo2C-0.05. The characterization of the catalytic performance of the catalyst for hydrogen production by water electrolysis is the same as that of example 1.
Example 5
The procedure and procedure for the preparation of example 5 are essentially the same as in example 1 above, except that: no manganese acetate (Mn (C) was added2H3O2)2·4H2O), the catalyst obtained is noted as Mn, N-Mo2And C-0. The characterization of the catalytic performance of the catalyst for hydrogen production by water electrolysis is the same as that of example 1.
Example 6
The procedure and procedure for the preparation of example 6 are essentially the same as in example 1 above, except that: the molar ratio of aniline to molybdenum atoms is 10:1, the molar concentration of molybdenum atoms is 1.0mol/L, and the molar ratio of Mn to Mo is 0.5. This sample was labeled sample a.
Example 7
The procedure and procedure for the preparation of example 7 are essentially the same as in example 1 above, except that: the molar ratio of aniline to molybdenum atoms is 1: 1, the molar concentration of molybdenum atoms is 0.3mol/L, and the molar ratio of Mn to Mo is 0.05. This sample was labeled sample B.
The following table 1 shows ICP-OES results of manganese contents of manganese-nitrogen co-doped molybdenum carbide nanorods prepared at different manganese-molybdenum ratios, indicating that manganese is successfully doped into molybdenum carbide crystals.
TABLE 1
FIG. 1 is an XRD (X-ray diffraction) diagram of manganese-nitrogen-codoped molybdenum carbide nanorods prepared by different manganese-molybdenum ratios, and it can be seen from FIG. 1 that the prepared catalyst is β -Mo2C, and the manganese doping in a certain content range does not influence the crystal composition.
FIG. 2 is an XRD pattern of sample A and sample B from FIG. 2 it can be seen that both sample A and sample B are β -Mo2C。
Fig. 3 is an SEM image (a) and a high power TEM image (b) of the manganese-nitrogen co-doped molybdenum carbide nanorods prepared in example 1, which are stacked with molybdenum carbide nanoparticles having uniform particle size, have rich pore structure, and have no lattice fringes of carbon under a high power transmission electron microscope.
Fig. 4 is a raman characterization of manganese-nitrogen co-doped molybdenum carbide nanorods prepared according to different manganese-molybdenum ratios, and a raman spectrum only has characteristic peaks of molybdenum carbide and characteristic peaks (D peak and G peak) without carbon, which indicates that the surface of the prepared catalyst is not covered by contaminated carbon.
FIG. 5 is an XPS survey spectrum of manganese-nitrogen co-doped molybdenum carbide nanorods prepared in example 1, and the nitrogen signal in the survey spectrum indicates that nitrogen is doped into the molybdenum carbide crystal.
FIG. 6 shows the characterization of the catalytic performance of manganese-nitrogen co-doped molybdenum carbide nanorods in hydrogen production by electrolyzing water, wherein (a) is a linear sweep voltammetry curve, and (b) is a Tafel curve. As can be seen from (a), when the current density was 20mA/cm2，Mn、N-Mo2C-0、Mn、N-Mo2C-0.001、Mn、 N-Mo2C-0.005、Mn、N-Mo2C-0.01、Mn、N-Mo2The overpotentials required for C-0.05 were 226mV, 208mV, 195mV, 192mV, 218mV, respectively, which indicates Mn, N-Mo2The catalytic performance of the C-0.01 hydrogen production by water electrolysis is the best. As can be seen from (b), Mn, N-Mo2C-0、Mn、 N-Mo2C-0.001、Mn、N-Mo2C-0.005、Mn、N-Mo2C-0.01、Mn、N-Mo2The Tafel slopes of C-0.05 are respectively 103mV/dec, 72mV/dec, 70mV/dec, 66mV/dec and 88mV/dec, which shows that the rate limiting steps are Volmer-Heyrovsky steps, wherein the Volmer-Heyrovsky steps are absorption-desorption steps of hydrogen protons in the hydrogen production process by electrolyzing water, and the rate limiting step of the reaction can be obtained according to the Tafel slopes, and the smaller the Tafel slope is, the better the reaction is.
FIG. 7 is a stability characterization (i-t curve) of manganese-nitrogen co-doped molybdenum carbide nanorod prepared in example 1 for hydrogen production by electrolyzing water, and after 24h operation, the current density is still maintained at 7.2mA/cm2And the other sides show good stability.
The above embodiments are merely preferred embodiments of the present invention, which are not intended to limit the scope of the present invention, and various changes may be made in the above embodiments of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The invention has not been described in detail in order to avoid obscuring the invention.
Claims (10)
1. The preparation method of the manganese-nitrogen co-doped molybdenum carbide nanorod is characterized by comprising the following steps of:
s1, adding a molybdenum source, manganese salt and aniline into water, and performing ultrasonic treatment to form a mixed turbid liquid, wherein the molar ratio of manganese atoms to molybdenum atoms is 0.001-0.5:1, and the molar ratio of aniline to molybdenum atoms is 1-10: 1;
s2, regulating the pH value of the mixed turbid liquid to 3-6 by adding inorganic acid, and reacting to obtain a manganese-modified molybdenum amine precursor;
and S3, calcining the manganese modified molybdenum amine precursor in a reductive calcining atmosphere to obtain the manganese-nitrogen co-doped molybdenum carbide nanorod without carbon on the surface.
2. The method according to claim 1, wherein the molar concentration of molybdenum atoms in the mixed turbid liquid is 0.1-1.0 mol/L.
3. The method according to claim 1, wherein the molybdenum source is at least one selected from ammonium heptamolybdate, sodium molybdate, and potassium molybdate.
4. The method according to claim 1, wherein the manganese salt is at least one selected from the group consisting of manganese acetate, manganese nitrate and manganese chloride.
5. The production method according to claim 1, wherein the inorganic acid is at least one selected from the group consisting of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid.
6. The method as claimed in claim 1, wherein in step S3, the calcination is carried out at a calcination temperature raised to 600-800 ℃ at a temperature raising rate of 2-10 ℃/min for 2-10 hours.
7. The method according to claim 1, wherein the calcining atmosphere is a mixed gas of an inert gas and hydrogen gas.
8. The method according to claim 7, wherein the hydrogen gas is contained in the calcination atmosphere in an amount of 0.05 to 0.25 by volume.
9. Manganese-nitrogen-codoped molybdenum carbide nanorod obtained according to the preparation method of any one of claims 1-8.
10. Use of the manganese-nitrogen co-doped molybdenum carbide nanorod according to claim 9 as an electrocatalyst.
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