CN110787823B - Three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particle as well as preparation method and application thereof - Google Patents
Three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particle as well as preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 24
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 24
- 239000011609 ammonium molybdate Substances 0.000 claims description 24
- 229940010552 ammonium molybdate Drugs 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 238000001132 ultrasonic dispersion Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003929 acidic solution Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 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
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal carbides Chemical class 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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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
-
- B01J35/33—
-
- B01J35/51—
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particle and a preparation method thereof, and the technical scheme mainly comprises the following steps: (1) dissolving a surfactant and a flower-shaped carbon sphere in water for ultrasonic dispersion, and adding molybdate into the water for ultrasonic dispersion until the molybdate is dissolved; (2) and (2) transferring the mixed solution obtained in the step (1) into a reaction kettle, carrying out hydrothermal reaction, then carrying out suction filtration, washing and drying, and carrying out high-temperature annealing treatment in an inert gas atmosphere to obtain the three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particles. The designed structure has ultrafine nano particles, a three-dimensional nitrogen-doped flower-shaped carbon framework and nitrogen doped into molybdenum carbide and the carbon framework simultaneously, and is beneficial to exposure of catalytic sites, rapid mass transfer and optimization of electronic structures, so that the catalytic hydrogen evolution performance of the electrocatalyst is effectively improved.
Description
Technical Field
The invention belongs to the field of catalytic materials, particularly belongs to the field of catalysts for hydrogen production by water electrolysis, and particularly relates to a three-dimensional nitrogen-doped flower-shaped carbon sphere loaded ultrafine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst, a preparation method thereof and application thereof in hydrogen production by water electrolysis under an acidic condition.
Background
With the progress of the times, the consumption of a large amount of fossil fuels and the brought environmental problems, we are forced to seek a clean renewable energy source to replace the fossil fuels. Thus, the development of efficient clean sustainable hydrogen energy technologies has attracted increasing attention. Electrocatalytic cracking of water is one of the most efficient methods for producing hydrogen. Currently, platinum-based materials are the most effective hydrogen evolution electrocatalysts (HER), but their low abundance, high cost, poor durability, limit their large-scale application. Therefore, exploring high efficiency, low cost electrocatalysts to reduce energy consumption and improve HER efficiency, such as non-noble metal HER catalysts of cobalt, nickel, iron, tungsten, molybdenum based materials, etc., has attracted great research interest.
So far, the electrocatalytic performance of Pt/C is the best and the stability is good. But Pt is not available on a large scale because of its small abundance on the earth and high price. The search for inexpensive and efficient non-platinum catalysts has become a focus of research for the scientists in the time. Among these catalysts, molybdenum carbide is considered a new class of HER electrocatalysts due to its platinum-like d-orbital. In the past decade, transition metal carbides, sulphides etc. have been reported as highly efficient electrocatalysts, especially transition metal carbides, such as molybdenum carbide (j. mater. chem.a,2017,5,4879), have significant catalytic activity due to its own unique electronic structure and platinoid properties. However, Mo obtained at high temperatures 2 C will usually inevitably aggregate, resulting in less exposed active sites. In addition, the stronger Mo-H bond strength limits desorption of adsorbed H (hads) to H 2 . These problems affect Mo 2 Performance of C-based electrocatalysts. To overcome these disadvantages, reduction of nanocrystalline size or optimization of Mo is being carried out 2 More effort has been made in the electronic structure of C. But molybdenum carbide also has many challenges as an electrocatalyst, such as low transmission efficiency of electrons and charges, high Mo-H bond energy which is not beneficial to hydrogen precipitation, easy agglomeration at high temperature and the like.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the first object of the invention is to provide a three-dimensional nitrogen-doped flower-shaped carbon sphere-loaded ultrafine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst.
A second object of the present invention is to provide a method for preparing the above electrocatalyst.
The third purpose of the invention is to provide an application of the electrocatalyst in water electrolysis hydrogen production.
In order to achieve the first object of the invention, the technical scheme of the invention comprises the following steps:
(1) dissolving a surfactant and a flower-shaped carbon sphere in water for ultrasonic dispersion, and adding molybdate into the water for ultrasonic dispersion until the molybdate is dissolved;
(2) and (2) transferring the mixed solution obtained in the step (1) into a reaction kettle, carrying out hydrothermal reaction, then carrying out suction filtration, washing and drying, and carrying out high-temperature annealing treatment in an inert gas atmosphere to obtain the three-dimensional nitrogen-doped flower-shaped carbon sphere-loaded superfine nitrogen-doped molybdenum carbide nano particles.
Further setting the mass ratio of the surfactant to the molybdate and the flower-shaped carbon spheres in the step (1)
1:3-1:2 and 1.5:1-3.5:1 respectively.
The molybdate in the step (1) is further set to be one or a combination of more of ammonium molybdate, sodium molybdate and potassium molybdate.
Further setting the ultrasonic dispersion time in the step (1) to be 30-60 min.
Further setting that the drying temperature in the step (2) is 60-120 ℃, and the drying time is 8-12 h.
Further setting is that the inert gas in the step (2) is a mixed gas of argon and ammonia, and the proportion of ammonia is 5-15%.
Further setting the annealing temperature in the step (2) to be 700-1000 ℃, the heating rate to be 1-5 ℃/min and the heat preservation to be 1-3 h.
The second purpose of the invention is to provide the three-dimensional nitrogen-doped flower-shaped carbon sphere-loaded ultrafine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst prepared by the preparation method.
A third object of the invention is the use of an electrocatalyst as described as an electrocatalyst in the electrolysis of water for the production of hydrogen.
The invention has the following beneficial effects:
1. according to the invention, flower-type carbon spheres, surfactants and ammonium molybdate solution with different mass ratios are loaded with molybdenum carbide by a hydrothermal synthesis method, and the surfactants play roles of Qiaolian-type carbon spheres and ammonium molybdate, so that molybdenum carbide nanoparticles in a product are uniformly dispersed on the pieces of the flower-type carbon spheres, the agglomeration phenomenon caused by high temperature is avoided, the size of the molybdenum carbide is reduced, and more active sites are exposed.
2. The thin petal wall of the flower-shaped carbon ball is beneficial to the permeation of electrolyte, increases the contact sites of the molybdenum carbide nano particles and the electrolyte and is convenient for electron transfer and charge transfer.
3. The ammonia gas introduced into the invention contains abundant nitrogen elements, and the nitrogen atoms are doped with the composite material after high-temperature annealing, so that the adsorption energy of hydrogen on the surface of the active substance is reduced, and the hydrogen is favorably separated out in the water electrolysis process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is an XRD pattern of a three-dimensional nitrogen-doped flower-type carbon sphere-supported ultrafine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst synthesized by the method of the present invention according to example 2 and comparative example three;
graph analysis: as can be seen from the figure, Mo is contained in the catalyst 2 C；
FIG. 2 is a scanning electron microscope and a high resolution picture of three-dimensional nitrogen-doped flower-shaped carbon sphere-loaded ultrafine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst;
graph analysis: the catalyst is a flower-shaped ball with the microscopic appearance of about 200 nm;
FIG. 3 is a three-dimensional nitrogen-doped flower-shaped carbon sphere-loaded ultrafine nitrogen-doped molybdenum carbide nanoparticle electrocatalystCatalytic hydrogen evolution performance and a schematic diagram. Wherein, 2.5Mo 2 C/NFCNS-800 is the sample of example 2, N-2.5Mo 2 C/NFCNS-800-10% is the sample of example 6;
graph analysis: left panel at 0.5M H 2 SO 4 In solution, commercial platinum/carbon catalyst (20% mass fraction), 2.5Mo in example 2 2 C/NFCNS-800 catalyst, for N-2.5Mo in example 6 2 Linear voltammetric testing of C/NFCNS-800-10% catalyst. It can be seen from the figure that N-2.5Mo is added to the alloy of example 6 2 The C/NFCNS-800-10% catalyst has the highest performance of catalytic hydrogen evolution, the initial overpotential is close to that of a commercial platinum/carbon catalyst, and the current density is 10mA/cm 2 The overpotential was 60 mV. And 2.5Mo in example 2 2 C/NFCNS-800 catalyst with current density of 10mA/cm 2 The overpotential was 82 mV.
The right graph is a tafel slope plot for the three catalysts described above (tafel formula: η ═ b log (j) + a, where j is the current density and b is the tafel slope). It can be seen from the figure that the Tafel slope for the commercial platinum/carbon catalyst is 30mV dec -1 2.5Mo in example 2 2 The Tafel slope of the C/NFCNS-800 catalyst was 39mV dec -1 The hydrogen evolution principle is shown to be Volmer-Heyrovsky, for N-2.5Mo in example 6 2 The Tafel slope of the C/NFCNS-800-10% catalyst was 31mV dec -1 It shows that the hydrogen evolution principle is Volmer-Tafel similar to that of platinum/carbon catalyst;
FIG. 4 is a graph of stability testing of a three-dimensional nitrogen-doped flower-shaped carbon sphere-loaded ultrafine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst;
graph analysis: at 0.5M H 2 SO 4 In solution at a voltage of between 0.05 and-0.45V at 100mV s -1 The cyclic voltammetry test was performed at the same rate. As can be seen from the figure, the cyclic voltammetry curves have little change after 10000 times and 12000 times of cycling, which indicates that the catalyst has extremely high stability. The timing current test of the catalyst is shown in the lower right corner of the figure, and the current density of the catalyst is hardly changed within 40 hours of the test, which also indicates that the catalyst has extremely high stability.
Detailed Description
To make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
sample preparation: dissolving 1g of flower-shaped carbon spheres and 1g of hexadecyl trimethyl ammonium bromide in 75mL of deionized water, uniformly dispersing, adding 1.5g of ammonium molybdate, ultrasonically dissolving and uniformly dispersing the ammonium molybdate, transferring the ammonium molybdate into a reaction kettle, reacting at 200 ℃ for 10 hours, cooling to room temperature, carrying out suction filtration and washing on the solution for three times, and transferring the solution into an oven at 80 ℃ to dry a sample. And then collecting solid powder, carrying out high-temperature annealing treatment in an argon atmosphere, heating to 800 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and then naturally cooling to obtain the three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst.
Electrocatalytic application: dissolving 2mg of sample and 1mg of conductive carbon in 500 mu L of alcohol-water mixed solution, carrying out ultrasonic treatment to uniformly mix the mixture to form black suspension, taking 10 mu L of suspension twice on a glassy carbon electrode, naturally airing the suspension, and then dropwise adding 5 mu L of Nafion with the mass fraction of 0.5%. In a three-electrode system (glassy carbon electrode as working electrode, saturated Ag/AgCl electrode as reference electrode, and platinum wire electrode as counter electrode), 0.5M H was added 2 SO 4 Solutions and 1m koh solution are electrolyte solutions to test the linear sweep voltammograms of the material. The current density of the sample was 10mA/cm 2 The overpotential in the acidic solution was 115 mV.
Example 2:
sample preparation: dissolving 1g of flower-shaped carbon spheres and 1g of hexadecyl trimethyl ammonium bromide in 75mL of deionized water, uniformly dispersing, adding 2.5g of ammonium molybdate, ultrasonically dissolving and uniformly dispersing the ammonium molybdate, transferring the ammonium molybdate into a reaction kettle, reacting at 200 ℃ for 10 hours, cooling to room temperature, carrying out suction filtration and washing on the solution for three times, and transferring the solution into an oven at 80 ℃ to dry a sample. And then collecting solid powder, carrying out high-temperature annealing treatment in an argon atmosphere, heating to 800 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and then naturally cooling to obtain the three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst.
Electrocatalytic application: the electrodes were prepared and tested as in example 1. The current density of the sampleIs 10mA/cm 2 The overpotential in the acidic solution was 82 mV.
Example 3:
sample preparation: dissolving 1g of flower-shaped carbon spheres and 1g of hexadecyl trimethyl ammonium bromide in 75mL of deionized water, uniformly dispersing, adding 3.5g of ammonium molybdate, ultrasonically dissolving and uniformly dispersing the ammonium molybdate, transferring the ammonium molybdate into a reaction kettle, reacting at 200 ℃ for 10 hours, cooling to room temperature, carrying out suction filtration and washing on the solution for three times, and transferring the solution into an oven at 80 ℃ to dry a sample. And then collecting solid powder, carrying out high-temperature annealing treatment in an argon atmosphere, heating to 800 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and then naturally cooling to obtain the three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst.
Electrocatalytic application: the electrodes were prepared and tested as in example 1. The current density of the sample was 10mA/cm 2 The overpotential in the acidic solution was 111 mV.
Example 4:
sample preparation: dissolving 1g of flower-shaped carbon spheres and 0.5g of hexadecyl trimethyl ammonium bromide in 75mL of deionized water, uniformly dispersing, adding 2.5g of ammonium molybdate, ultrasonically dissolving and uniformly dispersing the ammonium molybdate, transferring the ammonium molybdate into a reaction kettle, reacting for 10 hours at 200 ℃, cooling to room temperature, carrying out suction filtration and washing on the solution for three times, and transferring the solution into an oven at 80 ℃ to dry a sample. And then collecting solid powder, carrying out high-temperature annealing treatment in an argon atmosphere, heating to 800 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and then naturally cooling to obtain the three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst.
Electrocatalytic application: the electrodes were prepared and tested as in example 1. The current density of the sample was 10mA/cm 2 The overpotential in the acidic solution was 322 mV.
Example 5:
sample preparation: dissolving 1g of flower-shaped carbon spheres and 1.5g of hexadecyl trimethyl ammonium bromide in 75mL of deionized water, uniformly dispersing, adding 2.5g of ammonium molybdate, ultrasonically dissolving and uniformly dispersing the ammonium molybdate, transferring the ammonium molybdate into a reaction kettle, reacting for 10 hours at 200 ℃, cooling to room temperature, carrying out suction filtration and washing on the solution for three times, and transferring the solution into an oven at 80 ℃ to dry a sample. And then collecting solid powder, carrying out high-temperature annealing treatment in an argon atmosphere, heating to 800 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and then naturally cooling to obtain the three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst.
Electrocatalytic application: the electrodes were prepared and tested as in example 1. The current density of the sample was 10mA/cm 2 The overpotential was 97 mV.
Example 6:
sample preparation: dissolving 1g of flower-shaped carbon spheres and 1g of hexadecyl trimethyl ammonium bromide in 75mL of deionized water, uniformly dispersing, adding 2.5g of ammonium molybdate, ultrasonically dissolving and uniformly dispersing the ammonium molybdate, transferring the ammonium molybdate into a reaction kettle, reacting at 200 ℃ for 10 hours, cooling to room temperature, carrying out suction filtration and washing on the solution for three times, and transferring the solution into an oven at 80 ℃ to dry a sample. And then collecting solid powder, carrying out high-temperature annealing treatment in the atmosphere of argon and 10% ammonia gas, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and then naturally cooling to obtain the three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst.
Electrocatalytic application: the electrodes were prepared and tested as in example 1. The current density of the sample was 10mA/cm 2 The overpotential in acidity is 60mV, respectively. This sample is the best sample in the material control ratio.
In addition, a comparison table of hydrogen evolution performance of the catalyst in the invention and other molybdenum-based catalysts reported in the literature is attached, which shows that the material provided by the invention has excellent performance in the aspect of electrocatalytic hydrogen evolution.
TABLE 1 comparison of hydrogen evolution performance of the catalyst of the present invention with other molybdenum-based catalysts reported in the literature
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (3)
1. A preparation method of superfine nitrogen-doped molybdenum carbide nano particles loaded on three-dimensional nitrogen-doped flower-shaped carbon spheres is characterized by comprising the following steps:
dissolving 1g of flower-shaped carbon spheres and 1g of hexadecyl trimethyl ammonium bromide in 75mL of deionized water, uniformly dispersing, adding 2.5g of ammonium molybdate, ultrasonically dissolving and uniformly dispersing the ammonium molybdate, transferring the ammonium molybdate into a reaction kettle, reacting at 200 ℃ for 10 hours, cooling to room temperature, carrying out suction filtration and washing on the solution for three times, and transferring the solution into an oven at 80 ℃ to dry a sample; and then collecting solid powder, carrying out high-temperature annealing treatment in the atmosphere of argon and 10% ammonia gas, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and then naturally cooling to obtain the three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nanoparticle electrocatalyst.
2. The three-dimensional nitrogen-doped flower-shaped carbon sphere loaded ultrafine nitrogen-doped molybdenum carbide nano-particles prepared by the preparation method of claim 1.
3. The application of the three-dimensional nitrogen-doped flower-shaped carbon sphere-supported ultrafine nitrogen-doped molybdenum carbide nanoparticles as claimed in claim 2 in an electrocatalyst for hydrogen evolution by water electrolysis.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126876A (en) * | 2015-09-07 | 2015-12-09 | 复旦大学 | Flowerlike carbon-loaded MoS<2> nano-particle composite and preparation method thereof |
| CN105413729A (en) * | 2015-11-09 | 2016-03-23 | 中国科学技术大学 | Preparation method of nitrogen-doped carbon nanofiber aerogel with inlaid molybdenum carbide particles |
| CN107230782A (en) * | 2017-05-31 | 2017-10-03 | 青岛海澄知识产权事务有限公司 | A kind of preparation method of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate |
| CN107999108A (en) * | 2017-12-13 | 2018-05-08 | 中国石油大学(华东) | Molybdenum carbide or tungsten carbide catalyst of a kind of nitrogen-phosphor codoping carbon load and its preparation method and application |
| CN109675599A (en) * | 2018-12-05 | 2019-04-26 | 华南农业大学 | A kind of nitrogen-doped carbon cladding molybdenum carbide and its preparation method and application |
-
2019
- 2019-09-30 CN CN201910943949.8A patent/CN110787823B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126876A (en) * | 2015-09-07 | 2015-12-09 | 复旦大学 | Flowerlike carbon-loaded MoS<2> nano-particle composite and preparation method thereof |
| CN105413729A (en) * | 2015-11-09 | 2016-03-23 | 中国科学技术大学 | Preparation method of nitrogen-doped carbon nanofiber aerogel with inlaid molybdenum carbide particles |
| CN107230782A (en) * | 2017-05-31 | 2017-10-03 | 青岛海澄知识产权事务有限公司 | A kind of preparation method of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate |
| CN107999108A (en) * | 2017-12-13 | 2018-05-08 | 中国石油大学(华东) | Molybdenum carbide or tungsten carbide catalyst of a kind of nitrogen-phosphor codoping carbon load and its preparation method and application |
| CN109675599A (en) * | 2018-12-05 | 2019-04-26 | 华南农业大学 | A kind of nitrogen-doped carbon cladding molybdenum carbide and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| "Facile construction of N-doped Mo2C@CNT composites with 3D nanospherical structures as an efficient electrocatalyst for hydrogen evolution reaction";Wang Yali et al.;《IONICS》;20190418;第25卷(第9期);第4273-4283页 * |
| "Mo2C Nanoparticles Dispersed on Hierarchical Carbon Microflowers for Efficient Electrocatalytic Hydrogen Evolution";Huang Yang et al.，;《ACS NANO》;20161122;第10卷(第12期);第11337-11343页 * |
| "Surfactant-assisted hydrothermal synthesis of nitrogen doped Mo2C@C composites as highly efficient electrocatalysts for hydrogen evolution reaction";Liu Yuchuan et al.;《International Journal of Hydrogen Energy》;20190108;第44卷(第7期);第3702-3710页 * |
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