CN111617780A - Nitrogen-doped nickel-molybdenum-based composite sulfide for stably producing hydrogen by electrolyzing water and preparation method - Google Patents
Nitrogen-doped nickel-molybdenum-based composite sulfide for stably producing hydrogen by electrolyzing water and preparation method Download PDFInfo
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 72
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000002135 nanosheet Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 112
- 229910052759 nickel Inorganic materials 0.000 claims description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 229910052961 molybdenite Inorganic materials 0.000 claims description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 239000002120 nanofilm Substances 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 6
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 238000000643 oven drying Methods 0.000 description 7
- 239000010411 electrocatalyst Substances 0.000 description 6
- -1 transition metal sulfide Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
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- 238000001237 Raman spectrum Methods 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
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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
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
-
- 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 nitrogen-doped nickel-molybdenum-based composite sulfide for efficiently and stably producing hydrogen by electrolyzing water and a preparation method thereof. The material is a self-supporting micron rod array structure, wherein the surface of a micron rod is composed of a large number of overlapped ultrathin nano sheets, and N atoms are successfully doped into crystal lattices of nickel-molybdenum-based composite sulfides, so that the electron density of the material is changed. The catalyst is used as a working electrode for hydrogen production by water electrolysis, and shows excellent catalytic activity and stability. In addition, the catalyst has super-excellent stability, can stably work for 1000 hours and still keep the performance unchanged, and shows wide application prospects.
Description
Technical Field
The invention relates to the technical field of preparation of water electrolysis catalysts, in particular to a nitrogen-doped nickel-molybdenum-based composite sulfide for efficiently and stably producing hydrogen by water electrolysis and a preparation method thereof.
Background
Hydrogen is considered one of the most promising clean energy sources to solve energy crisis and environmental problems due to its high energy density and no pollution to the environment. Electrolysis of water is an efficient and economical way to achieve the production of high purity hydrogen. In order to improve the efficiency of hydrogen production by water electrolysis, it is necessary to develop an efficient and stable electrocatalyst for reducing the overpotential of the hydrogen evolution reaction. At present, the best electrocatalyst for hydrogen production by water decomposition is a platinum-based catalyst, but the low storage capacity of the material on the earth causes higher cost, and the poor stability also causes one of the reasons limiting the large-scale application of the material. Therefore, the development of non-noble metal catalysts having hydrogen production effects comparable to those of platinum-based catalysts has become a hot point of international research.
The transition metal sulfide shows good electrocatalytic hydrogen production activity due to the ideal atomic structure and two-dimensional layered crystal structure. Recently, the bimetallic sulfide not only combines the excellent catalytic activity of each metal sulfide, but also the synergistic effect of the metal sulfides is beneficial to the improvement of the catalytic performance, and the bimetallic sulfide is expected to become a high-efficiency electrocatalyst for replacing noble metals. The nickel-molybdenum-based sulfide has abundant active sites, and has the electrochemical properties of both nickel-based sulfide and molybdenum-based sulfide, so that the nickel-molybdenum-based sulfide is widely researched by people. For example, Yaqing Yang et al (ACS Catal.2017,7,2357-2-Ni3S2The heterostructure nanorod is used for hydrogen production by water electrolysis. However, the efficiency of hydrogen production by water electrolysis of nickel molybdenum based sulfide reported at present is still far lower than that of platinum based materials, and the stability of these catalysts can not meet the industrial requirements.
In addition, some researches in recent years show that doping hetero atoms into the electrocatalyst is beneficial to improving the activity of the electrocatalyst in hydrogen production by water electrolysis. The introduction of non-metallic heteroatoms with stronger electronegativity into the catalyst is beneficial to adjusting the electron density and the d-band center (nat. Commun.2018, 9:1425) of the catalyst, so that the adsorption and dissociation of water and the adsorption/desorption behavior of hydrogen (ACS Catal.2019, 9: 3744-. Therefore, if some atoms with stronger electronegativity can be introduced into the crystal lattice of the nickel-molybdenum-based composite sulfide to adjust the electron density and the d-band center of the nickel-molybdenum-based composite sulfide, the efficiency of hydrogen production by water electrolysis can be greatly improved, and bright prospects are brought for the practical application of the nickel-molybdenum-based composite sulfide.
Disclosure of Invention
The invention aims to provide a non-noble metal electrocatalyst for efficiently and stably electrolyzing water to prepare hydrogen, in particular to a nitrogen-doped nickel-molybdenum-based composite sulfide material and a preparation method thereof.
A composite N-doped Ni-Mo sulfide material is prepared from MoS2NiS and NiS2The nano-particles are composed of phases, are doped with nitrogen, and are self-supporting micro-rod arrays, wherein the surfaces of the micro-rods are composed of a large number of overlapped ultrathin nano-sheets, and the thickness of the nano-sheets is 5-15 nm.
According to the scheme, the nitrogen-doped nickel-molybdenum-based composite sulfide is formed by doping nitrogen in MoS2NiS and NiS2The crystal lattice of (2) has a rich interface between the phases.
According to the scheme, the diameter of the micron rod is 1.0-1.5 mu m.
According to the scheme, the nitrogen content of the nitrogen-doped nickel-molybdenum-based composite sulfide is 0.82-6.9%.
According to the scheme, the nitrogen-doped nickel-molybdenum-based composite sulfide grows on the foamed nickel substrate.
The preparation method of the nitrogen-doped nickel-molybdenum-based composite sulfide material comprises the following steps: soaking a nickel-molybdenum precursor micron rod array growing on commercial foam nickel in a urea solution, and then drying; and then, taking sulfur powder as a sulfur source, and carrying out a vulcanization reaction in an inert atmosphere to prepare the nitrogen-doped nickel-molybdenum-based composite sulfide.
According to the scheme, the concentration of the urea solution is 0.2-1.0 mol/L.
According to the scheme, the nickel-molybdenum precursor micron rod array is soaked in the urea solution for 2-12 hours.
According to the scheme, the drying temperature is 40-80 ℃, and 60 ℃ is preferred
According to the scheme, the area ratio of the sulfur powder to the nickel-molybdenum precursor micron rod array is 1: 1-1: 4(g: cm)2)。
According to the scheme, the temperature of the vulcanization reaction is 350-450 ℃, and the time is 1.0-3.0 h.
According to the scheme, the synthesis method of the nickel-molybdenum precursor micron rod comprises the following steps: will be (NH)4)6Mo7O24·4H2Dissolving O and nickel source substances in deionized water, and stirring to form a uniform solution; transferring the solution to a hydrothermal kettle liner, obliquely placing the cleaned commercial nickel foam in the hydrothermal kettle liner and completely immersing the commercial nickel foam in the solution, and then sealing the hydrothermal kettle for hydrothermal reaction; and after the reaction is finished, taking out the foamed nickel and cleaning to obtain the nickel-molybdenum precursor micron rod array.
According to the scheme, the nickel source material is selected from Ni (NO)3)2·6H2O、NiCl2·6H2O、NiSO4·6H2O。
In the above scheme, (NH) in the solution4)6Mo7O24·4H2The concentration of O is 0.005-0.02M; the concentration of nickel source substance is 0.02-0.08M, (NH)4)6Mo7O24·4H2The concentration ratio of O to the nickel source material is preferably 1: 4.
According to the scheme, the temperature of the hydrothermal reaction is 120-180 ℃, and the time is 6-12 hours.
The nitrogen-doped nickel-molybdenum-based composite sulfide is used as a stable catalyst for hydrogen production by water electrolysis in the application of hydrogen evolution by water electrolysis, and the specific application method comprises the following steps: in a KOH solution, nitrogen-doped nickel-molybdenum-based composite sulfide is used as a hydrogen evolution electrode in a three-electrode system and is used for electrolyzing water to evolve hydrogen.
According to the scheme, the potential of hydrogen evolution is preferably-0.1V vs. RHE, and the stable and efficient water electrolysis can be realized for a long time (up to 1000 h).
According to the invention, a nitrogen source is introduced by a urea soaking method for the first time, and then the nitrogen-doped nickel-molybdenum-sulfur composite sulfide micron rod is obtained by a calcination and vulcanization method. A series of characterization tests prove that N atoms in the nitrogen-doped nickel-molybdenum-based composite sulfide provided by the invention are successfully doped into crystal lattices of the nickel-molybdenum-based composite sulfide, the electron density of the material is changed, rich interfaces are formed among phases, and the interfaces can reconfigure an electronic structure, so that hydrogen is produced by efficiently and stably electrolyzing water. Ultimately resulting in good hydrogen production activity by electrolysis of water.
The invention has the beneficial effects that:
the nitrogen-doped nickel-molybdenum-based composite sulfide catalyst provided by the invention is used as a working electrode for hydrogen production by water electrolysis, shows excellent catalytic activity and is 10,500 and 1000mA cm under current density-2The overpotential required can be as low as 68, 250 and 322mV, far below standard noble metals and other transition metal sulfides reported. In addition, the catalyst has excellent stability, can continuously work for 1000 hours without performance attenuation, and shows wide application prospect.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of a nickel molybdenum precursor.
FIG. 2 is an SEM image of a nitrogen-doped nickel-molybdenum-based complex sulfide (N-NiMoS for short).
Fig. 3 is an SEM image of pure nickel molybdenum-based complex sulfide (NiMoS for short).
FIG. 4 is a comparison of the characterization of NiMoS and N-NiMoS: (a) an X-ray diffraction spectrum (XRD) pattern, and a Raman spectrum (Raman) pattern.
FIGS. 5(a) - (c) are high resolution XPS spectra comparisons of Ni2p, Mo3d, and S2p for NiMoS and N-NiMoS, respectively; FIG. (d) is a high resolution XPS spectrum of N1s from N-NiMoS.
FIG. 6 is a Transmission Electron Microscope (TEM) image of N-NiMoS: (a) TEM images at low magnification; (b) is a high-resolution TEM image; (c) selected Area Electron Diffraction (SAED) pattern for N-NiMoS; (d) (ii) to (i) are distribution diagrams of the elements corresponding to N-NiMoS, respectively.
FIG. 7 is a graph of catalytic performance of the catalyst: commercial Pt/C, NiMoS and N-NiMoS (a) Linear Sweep Voltammogram (LSV) vs.b at current densities of 10,500 and 1000mA cm-2Overpotential contrast graph of time; (c) comparison of LSV curves of N-NiMoS before and after 3000 CV cycles; (d) current response plot of N-NiMoS at-0.1V vs. RHE.
Detailed Description
Example 1
(1) Commercial nickel foam (2 × 5cm 5)2) Placing in 3M HCl solution, ultrasonic treating for 15min, washing with deionized water, ultrasonic treating in anhydrous alcohol for 5min, washing with deionized water, and oven drying.
(2) 0.798g of Ni (NO)3)2·6H2O and 0.742g (NH)4)6Mo7O24·4H2O was added to a beaker containing 60mL of deionized water and stirred for 10 min. Transferring the obtained clear solution into a 100mL polytetrafluoroethylene hydrothermal kettle liner, obliquely placing the treated commercial nickel foam into the hydrothermal kettle liner and completely immersing the commercial nickel foam into the solution, sealing the hydrothermal kettle, and heating the hydrothermal kettle in an oven at 150 ℃ for 6 hours. And after the reaction is finished, cooling to room temperature, opening the hydrothermal kettle, taking out the foamed nickel, washing the foamed nickel with deionized water for about 1min, and then drying the foamed nickel in an oven for 6h to obtain the nickel-molybdenum precursor growing on the foamed nickel. The electron micrograph in fig. 1 shows that the nanostructure of the nickel molybdenum precursor is a micron rod with a smooth surface.
(3) Taking the foamed nickel (1 × 2 cm) obtained in the step (2) and growing the nickel-molybdenum micron rod precursor for introducing the nitrogen source2) Soaking in 0-1.0M (0, 0.2, 0.5, 1mol/L) urea solution for 6h, taking out, and drying in an oven.
(4) 2g of sulfur powder was weighed, ground, placed in a crucible, and placed upstream of a tube furnace. Placing the foamed nickel obtained in the step (3) in another crucible and placing the crucible at the downstream of the tube furnace, and then placing the crucible in N2Heating to 400 ℃ at the speed of 5 ℃/min under the atmosphere, and preserving the heat for 2h to obtain the nitrogen-doped nickel-molybdenum-based composite sulfide.
In a 1M KOH solution, a nitrogen-doped nickel-molybdenum-based composite sulfide is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, and a graphite rod is used as a counter electrode, so that the electrochemical performance and characterization test is carried out. Table 1 shows the comparison of catalytic performance of the nitrogen-doped nickel-molybdenum-based composite sulfide prepared by soaking the nickel-molybdenum precursor in urea solutions with different concentrations in example 1. The nitrogen-doped nickel-molybdenum-based composite sulfide is represented by N-NiMoS, and the pure nickel-molybdenum-based composite sulfide is represented by NiMoS.
FIG. 2 is an electron microscope image of N-NiMoS, showing that the material is a self-supporting micron rod array, wherein the surface of the micron rod is composed of a large number of overlapped ultrathin nano sheets, and the thickness of the nano sheets is 5-15 nm. Fig. 3 is an electron micrograph of NiMoS showing the same nanostructure as N-NiMoS, illustrating that the N-doping does not change the morphology of NiMoS. FIG. 4(a) is an XRD diagram showing the formation of NiMoS from MoS as a nickel-molybdenum-based sulfide complex2NiS and NiS2The phase composition of the mixture, and the incorporation of N did not alter the phase of NiMoS. While in the XRD pattern of N-NiMoS, NiS2The (002) plane of NiS, the (102) plane of NiS and the (100) plane of MoS2 are all shifted at high angles relative to NiMoS, since N atoms with smaller radii replace S atoms, indicating that N atoms are successfully incorporated into the crystal lattice of NiMoS. Fig. 4(c) the raman spectra of N-NiMoS are shifted from NiMoS, further illustrating the distortion of the crystal lattice caused by the successful doping of N atoms into the crystal lattice of NiMoS. As can be seen from X-ray photoelectron spectroscopy (XPS) of fig. 5, after nitrogen doping, the valence states of Ni, Mo and S are all increased because a small amount of N replaces part of the S position, so that electrons flow around N atoms having more electronegativity, resulting in a decrease in electrons around Ni, Mo and S. While N1s of fig. 5(d) also re-verifies the presence of N, these characterizations all demonstrate that N is successfully incorporated into the NiMoS lattice.
The TEM image shown in fig. 6(a) is a nanostructure at one end of a single N-NiMoS cuboid, covered by a large number of overlapping interleaved ultrathin nanoflakes. FIG. 6(b) shows a high resolution TEM image of N-NiMoS with lattice fringes at d 0.296nm and 0.254nm corresponding to the (100) crystal plane of NiS and NiS, respectively2The (d) 0.227 and the interlayer spacing of 0.266nm respectively correspond to MoS2The (103) and (101) crystal planes of (a), which indicates that the structural phase can be maintained after N doping. In addition, interfaces are formed among the crystal faces, which are favorable for chemical adsorption of hydrogen, so that the hydrogen evolution reaction is promoted. The electron diffraction (SAED) pattern of N-NiMoS also demonstrates the (102) crystal plane of NiS, NiS2(-111), (121) and (222) crystal planes of (A) and MoS2Presence of (002), (100) and (104) crystal planes of (a). FIG. 6(d) to (i) shows the distribution diagram of elementsShows that Mo, Ni, S and N elements are uniformly distributed in the N-NiMoS micron rod.
Fig. 7 shows the results of electrochemical performance tests. FIG. 7(a) shows that the hydrogen production performance by water electrolysis of N-NiMoS is significantly better than that of pure NiMoS. Although the overpotential at low current densities is slightly greater than commercial Pt/C, the performance of N-NiMoS is far superior to commercial Pt/C when the overpotential exceeds 190 mV. FIG. 7(b) shows in detail the catalysts at 10,500 and 1000mA cm-2Overpotential at current density. At 10mA cm-2The overpotential of N-NiMoS is only 68mV at current density of (1 mV), which is better than that of pure NiMoS (102mV), and is very close to that of commercial Pt/C (50 mV). Furthermore, at 500 and 1000mA cm-2The N-NiMoS electrode possessed the lowest overpotentials of 250 and 322mV, much lower than NiMoS (311 and 436 mV) and Pt/C (303 and 456 mV). Fig. 7(c) shows the LSV curves before and after 3000 cycles of N-NiMoS in the interval 0 to-0.2V vs. rhe, the two curves being substantially coincident, which illustrates its excellent stability. FIG. 7 (d) shows the continuous electrolysis of N-NiMoS for hydrogen production for 1000h at a potential of-0.1V vs. RHE, again illustrating its superior stability.
TABLE 1
Example 2
(1) Commercial nickel foam (2.5 × 4cm 4)2) Placing in 3M HCl solution, ultrasonic treating for 15min, washing with deionized water, ultrasonic treating in anhydrous alcohol for 5min, washing with deionized water, and oven drying.
(2) 0.570g of NiCl2·6H2O and 0.742g (NH)4)6Mo7O24·4H2O was added to a beaker containing 60mL of deionized water and stirred for 10 min. Transferring the obtained clear solution into a 100mL polytetrafluoroethylene hydrothermal kettle liner, obliquely placing the treated commercial nickel foam into the hydrothermal kettle liner and completely immersing the commercial nickel foam into the solution, sealing the hydrothermal kettle, and heating the hydrothermal kettle in an oven at 180 ℃ for 6 hours. After the reaction is finished and the temperature is cooled to the room temperature, the hydrothermal kettle is opened, and the foamed nickel is taken outAnd (4) taking out, washing with deionized water for about 1min, and then placing in an oven for drying for 6h to obtain the nickel-molybdenum precursor growing on the foamed nickel.
(3) Taking the foamed nickel (1 × 2 cm) obtained in the step (2) and growing the nickel-molybdenum micron rod precursor for introducing the nitrogen source2) Soaking in 0.5M urea solution for 4h, taking out, and oven drying.
(4) 2.5g of sulfur powder was weighed, ground, placed in a crucible, and placed upstream of a tube furnace. Placing the foamed nickel obtained in the step (3) in another crucible and placing the crucible at the downstream of the tube furnace, and then placing the crucible in N2Heating to 400 ℃ at the speed of 5 ℃/min under the atmosphere, and preserving the heat for 2h to obtain the nitrogen-doped nickel-molybdenum-based composite sulfide.
In a 1M KOH solution, a nitrogen-doped nickel-molybdenum-based composite sulfide is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, and a graphite rod is used as a counter electrode, so that the electrochemical performance and characterization test is carried out. Current densities of 10,500 and 1000 mAcm-2The overpotential of time is detailed in table 2.
Example 3
(1) Commercial nickel foam (3 × 3 cm)2) Placing in 3M HCl solution, ultrasonic treating for 15min, washing with deionized water, ultrasonic treating in anhydrous alcohol for 5min, washing with deionized water, and oven drying.
(2) 0.399g of Ni (NO)3)2·6H2O and 0.371g (NH)4)6Mo7O24·4H2O was added to a beaker containing 60mL of deionized water and stirred for 10 min. Transferring the obtained clear solution into a 100mL polytetrafluoroethylene hydrothermal kettle liner, obliquely placing the treated commercial nickel foam into the hydrothermal kettle liner and completely immersing the commercial nickel foam into the solution, sealing the hydrothermal kettle, and heating the hydrothermal kettle in an oven at 160 ℃ for 8 hours. And after the reaction is finished and the temperature is cooled to room temperature, opening the hydrothermal kettle, taking out the foamed nickel, washing the foamed nickel with deionized water for about 1min, and then drying the foamed nickel in an oven for 6h to obtain the nickel-molybdenum precursor growing on the foamed nickel.
(3) Taking the foamed nickel (1 × 2 cm) obtained in the step (2) and growing the nickel-molybdenum micron rod precursor for introducing the nitrogen source2) Soaking in 0.5M urea solution for 8h, taking out, and oven drying.
(4) 2g of sulfur powder was weighed, ground, placed in a crucible, and placed upstream of a tube furnace. Placing the foamed nickel obtained in the step (3) in another crucible and placing the crucible at the downstream of the tube furnace, and then placing the crucible in N2Heating to 400 ℃ at the speed of 5 ℃/min under the atmosphere, and preserving the heat for 2h to obtain the nitrogen-doped nickel-molybdenum-based composite sulfide.
In a 1M KOH solution, a nitrogen-doped nickel-molybdenum-based composite sulfide is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, and a graphite rod is used as a counter electrode, so that the electrochemical performance and characterization test is carried out. Current densities of 10,500 and 1000 mAcm-2The overpotential of time is detailed in table 2.
Example 4
(1) Commercial nickel foam (2 × 5cm 5)2) Placing in 3M HCl solution, ultrasonic treating for 15min, washing with deionized water, ultrasonic treating in anhydrous alcohol for 5min, washing with deionized water, and oven drying.
(2) 0.631g of NiSO4·6H2O and 0.742g (NH)4)6Mo7O24·4H2O was added to a beaker containing 60mL of deionized water and stirred for 10 min. Transferring the obtained clear solution into a 100mL polytetrafluoroethylene hydrothermal kettle liner, obliquely placing the treated commercial nickel foam into the hydrothermal kettle liner and completely immersing the commercial nickel foam into the solution, sealing the hydrothermal kettle, and heating the hydrothermal kettle in an oven at 180 ℃ for 6 hours. And after the reaction is finished and the temperature is cooled to room temperature, opening the hydrothermal kettle, taking out the foamed nickel, washing the foamed nickel with deionized water for about 1min, and then drying the foamed nickel in an oven for 6h to obtain the nickel-molybdenum precursor growing on the foamed nickel.
(3) Taking the foamed nickel (1 × 2 cm) obtained in the step (2) and growing the nickel-molybdenum micron rod precursor for introducing the nitrogen source2) Soaking in 0.5M urea solution for 6h, taking out, and oven drying.
(4) 1.5g of sulfur powder was weighed, ground, placed in a crucible, and placed upstream of a tube furnace. Placing the foamed nickel obtained in the step (3) in another crucible and placing the crucible at the downstream of the tube furnace, and then placing the crucible in the tube furnaceIn N2Heating to 350 ℃ at the speed of 5 ℃/min under the atmosphere, and preserving the heat for 2h to obtain the nitrogen-doped nickel-molybdenum-based composite sulfide.
In a 1M KOH solution, a nitrogen-doped nickel-molybdenum-based composite sulfide is used as a working electrode, an Hg/HgO electrode is used as a reference electrode, and a graphite rod is used as a counter electrode, so that the electrochemical performance and characterization test is carried out. Current densities of 10,500 and 1000 mAcm-2The overpotential of time is detailed in table 2.
TABLE 2
Claims (10)
1. The nitrogen-doped nickel-molybdenum-based composite sulfide is characterized in that: the material consists of MoS2NiS and NiS2The nano-film is composed of a phase, is doped with nitrogen, and is in a self-supporting micro-rod array structure, wherein the surface of the micro-rod is composed of a large number of overlapped ultrathin nano-sheets, and the thickness of the nano-sheets is 5-15 nm.
2. The phase composition of the nitrogen-doped nickel molybdenum-based composite sulfide according to claim 1, characterized in that: nitrogen doped in MoS2NiS and NiS2And rich interfaces are formed between the phases; the diameter of the micron rod is 1.0-1.5 μm.
3. The nitrogen-doped nickel-molybdenum-based complex sulfide of claim 1, wherein: the nitrogen-doped nickel-molybdenum-based composite sulfide grows on the foamed nickel substrate; the nitrogen content of the nitrogen-doped nickel-molybdenum-based composite sulfide is 0.82-6.9%.
4. The application of the nitrogen-doped nickel-molybdenum-based composite sulfide as the high-efficiency and stable catalyst for hydrogen production by water electrolysis in the claim 1 comprises the following steps: the nitrogen-doped nickel-molybdenum-based complex sulfide as claimed in claim 1 is used as a hydrogen evolution electrode in a three-electrode system in a KOH solution for electrolysis of water for hydrogen evolution.
5. The method for producing a nitrogen-doped nickel-molybdenum-based composite sulfide according to claim 1, characterized in that: soaking a nickel-molybdenum precursor micron rod array growing on commercial nickel foam in a urea solution, and then drying in an oven at the temperature of 40-80 ℃; and then, taking sulfur powder as a sulfur source, and carrying out a vulcanization reaction in an atmosphere furnace in an inert atmosphere to prepare the nitrogen-doped nickel-molybdenum-based composite sulfide.
6. The method for producing a nitrogen-doped nickel-molybdenum-based sulfide complex according to claim 5, wherein: the concentration of the urea solution is 0.2-1.0 mol/L; the nickel-molybdenum precursor micron rod array is soaked in the urea solution for 2-12 hours.
7. The method for producing a nitrogen-doped nickel-molybdenum-based sulfide complex according to claim 5, wherein: the area ratio of the sulfur powder used in the vulcanization reaction to the nickel-molybdenum precursor micron rod array is 1: 1-1: 4(g: cm)2)。
8. The method for producing a nitrogen-doped nickel-molybdenum-based sulfide complex according to claim 5, wherein: the temperature used in the vulcanization calcining process is 350-450 ℃, and the time is 1.0-3.0 h.
9. The method for producing a nitrogen-doped nickel-molybdenum-based sulfide complex according to claim 5, wherein: the synthesis method of the nickel-molybdenum precursor comprises the following steps: will be (NH)4)6Mo7O24·4H2Dissolving O and nickel source substances in deionized water, and stirring to form a uniform solution; transferring the solution to a hydrothermal kettle liner, obliquely placing the cleaned commercial nickel foam in the hydrothermal kettle liner and completely immersing the commercial nickel foam in the solution, sealing the hydrothermal kettle, and carrying out hydrothermal reaction in an oven; and after the reaction is finished, taking out the foamed nickel and cleaning to obtain the nickel-molybdenum precursor.
10. The nitrogen-doped nickel-molybdenum-based composite of claim 9The synthetic method of the synthetic sulfide is characterized by comprising the following steps: the nickel source is selected from Ni (NO)3)2·6H2O、NiCl2·6H2O、NiSO4·6H2O; in said solution (NH)4)6Mo7O24·4H2The concentration of O is 0.005-0.02M; the concentration of the nickel source substance is 0.02-0.08M, the temperature of the hydrothermal reaction is 120-180 ℃, and the time is 6-12 h.
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