CN114561649B - Iron-modified nickel hydroxy sulfide ultrathin nanosheet array, preparation method and application thereof - Google Patents
Iron-modified nickel hydroxy sulfide ultrathin nanosheet array, preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 73
- KRIFFYDANHCLPO-UHFFFAOYSA-N nickel sulfanediol Chemical class S(O)O.[Ni] KRIFFYDANHCLPO-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 11
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 5
- 238000006056 electrooxidation reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002064 nanoplatelet Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002588 FeOOH Inorganic materials 0.000 claims description 2
- BIBNGXLKRYORSJ-UHFFFAOYSA-M [Ni+]=S.[OH-] Chemical class [Ni+]=S.[OH-] BIBNGXLKRYORSJ-UHFFFAOYSA-M 0.000 claims description 2
- -1 iron modified nickel hydroxysulfide Chemical class 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 239000006260 foam Substances 0.000 description 14
- 229910019931 (NH4)2Fe(SO4)2 Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000004098 selected area electron diffraction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to an iron-modified nickel hydroxysulfide ultrathin nanosheet array, a preparation method and application thereof. The material is an amorphous iron-modified nickel hydroxysulfide nano-sheet array grown on a bulk nickel substrate. The preparation method is simple and efficient, and the doping of iron is beneficial to improving the conductivity of the catalyst and the transfer capacity of electrons, so that the Oxygen Evolution Reaction (OER) of electrolytic water is promoted. The catalyst exhibits excellent OER catalytic activity at current densities of 10,100 and 500mA cm ‑2 At the time, the minimum required overpotential can be 221, 265 and 322mV, which is far lower than that of the pure nickel hydroxysulfide ultrathin nano-sheet array. Meanwhile, the catalyst can be used for preparing the catalyst at 10-500 mA cm ‑2 Is operated stably at a current density of (3).
Description
Technical Field
The invention relates to the technical field of electrolytic water oxygen production catalysts, in particular to an iron-modified nickel hydroxysulfide ultrathin nanosheet array, a preparation method and application thereof.
Background
Because of the advantages of high energy density of hydrogen and friendly products, the electrolysis of water to produce hydrogen becomes one of the leading-edge scientific methods for solving the problems of energy and environment. The electrolyzed water consists of two half reactions, hydrogen Evolution (HER) and Oxygen Evolution (OER), respectively. In both half reactions, OER on the anode becomes a major bottleneck limiting hydrogen production by electrolysis of water due to slow kinetics. Although Ru/Ir based catalysts exhibit very good OER activity, their large scale application is hindered by scarce resources, high cost and poor stability at high current densities. Therefore, there is an urgent need to develop efficient, low-cost catalysts from earth-rich resources.
Among the catalysts reported in the past, transition metal hydroxides have been attracting attention due to their low cost, unique crystal structure and effective OER activity, but their limited specific surface area and poor intrinsic conductivity have resulted in inefficient transport of electrons, resulting in excessive overpotential and thus consumption of a large amount of electrical energy. Several effective strategies have been used to increase the OER activity of these catalysts, such as preparing specific nanostructures to increase the number of catalytically active sites, doping heteroatoms to effectively increase the intrinsic activity of the catalyst. And the S-doped metal hydroxide or hydroxy metal sulfide (such as NiSOH and the like) obtained by derivatization has a good catalytic effect. Wherein, the sulfur atom not only can regulate the electronic structure of the metal, but also can influence the adsorption strength of the intermediate active substance on the active site, thereby facilitating the adsorption and desorption (Adv.Mater.2018, 30,1800757;Nat.Commun.2020,11,5075). However, the reported nickel hydroxysulfide still has the problems of high overpotential, poor stability and the like, and the preparation process is complex, the energy consumption is high and the like, so that the cost is further increased. Therefore, if a simple preparation method can be developed to modify the nickel hydroxysulfide, the OER activity of the catalyst can be effectively improved, the cost can be reduced, and the commercial application of the catalyst can be accelerated.
Disclosure of Invention
In order to solve the problems, the invention aims to provide an efficient OER catalyst and a simple preparation method thereof, in particular to an iron-modified nickel hydroxysulfide ultrathin nanosheet array and a preparation method thereof.
An iron-modified nickel hydroxysulfide ultrathin nanosheet array is an amorphous iron-modified nickel hydroxysulfide nanosheet array grown on a bulk nickel substrate.
According to the scheme, the thickness of the iron-modified nickel hydroxysulfide nano-sheets in the iron-modified nickel hydroxysulfide ultra-thin nano-sheet array is 3-8 nm, and the iron content is 2.5-7.2% (atomic percent).
According to the scheme, the iron-modified ultra-thin nickel hydroxysulfide nano-sheet array is prepared by a two-step oxidation method, wherein bulk nickel is used as a nickel source and a substrate, the ultra-thin nickel hydroxysulfide nano-sheet array is prepared by a wet chemical oxidation process, and the ultra-thin nickel hydroxysulfide nano-sheet array is prepared by an anodic oxidation process.
The preparation method of the iron-modified nickel hydroxysulfide ultrathin nanosheet array comprises the following steps:
step (1): immersing bulk nickel in persulfate and thiosulfate solutions for ice bath reaction of the ultra-thin nickel hydroxysulfide nano-sheet array;
step (2): the preparation method for preparing the iron-modified hydroxyl nickel sulfide ultrathin nanosheet array by electrochemical anodic oxidation comprises the following steps: and (3) taking the ultra-thin nickel hydroxysulfide nano-sheet array obtained in the step (1) as a working electrode, taking ferrous source substances as electrolyte, and performing electrochemical oxidation reaction to obtain the iron-modified ultra-thin nickel hydroxysulfide nano-sheet array.
According to the scheme, the bulk nickel can be any type of nickel, such as foam nickel, nickel flakes, nickel mesh and the like.
According to the above scheme, the persulfate is selected from (NH) 4 ) 2 S 2 O 8 ，Na 2 S 2 O 8 ，K 2 S 2 O 8 The method comprises the steps of carrying out a first treatment on the surface of the Thiosulfate is selected from Na 2 S 2 O 3 ，K 2 S 2 O 3 ，(NH 4 ) 2 S 2 O 3 。
According to the scheme, the concentration of the persulfate in the mixed solution of the persulfate and the thiosulfate is 0.05-0.15 mol/L; the concentration of thiosulfate is 0.015-0.05 mol/L.
According to the scheme, before the ice bath reaction in the step (1), the mixed solution of persulfate and thiosulfate is subjected to precooling treatment in an ice bath.
According to the scheme, the persulfate is added with deionized water to prepare a solution, and then thiosulfate is added and stirred to obtain a mixed solution of persulfate and thiosulfate.
According to the scheme, after the reaction in the step (1) is finished, the bulk nickel is washed clean by deionized water, and the ultra-thin nano sheet array of the nickel hydroxysulfide is obtained after natural drying.
According to the scheme, the ice bath reaction time of the step (1) is 4-12 min.
According to the scheme, the step (2) is to perform electrochemical oxidation reaction under constant positive current density.
According to the scheme, the constant current in the step (2)The density is 1-12 mA cm -2 。
According to the scheme, in the step (2), the counter electrode is a graphite rod electrode, and the electrolyte is (NH) 4 ) 2 Fe(SO 4 ) 2 A solution. After the reaction is finished, washing with deionized water, and airing at room temperature to obtain the iron-modified nickel hydroxy sulfide ultrathin nanosheet array.
According to the above scheme, in the step (2) (NH 4 ) 2 Fe(SO 4 ) 2 The concentration of the solution is 0.005-0.02 mol/L.
According to the scheme, the reaction time of the step (2) is 10-60 min.
The application of the iron-modified nickel hydroxy sulfide ultrathin nanosheet array as an efficient and stable electrolytic water oxygen production catalyst in oxidizing water comprises the following specific application methods: an iron-modified nickel hydroxysulfide ultrathin nanosheet array is used as an oxygen evolution electrode in an alkaline three-electrode system and is used for electrocatalytically oxidizing water.
The invention has the beneficial effects that:
1. the invention innovatively develops a simple two-step oxidation preparation method for the first time. Firstly preparing an ultrathin nickel hydroxysulfide nano-sheet array by a wet chemical oxidation method, and finally obtaining the amorphous iron-modified ultrathin nickel hydroxysulfide nano-sheet array by an anodic oxidation method. The self-supporting ultrathin amorphous nano-sheet is composed of self-supporting ultrathin nano-sheets, the thickness of the ultrathin nano-sheets is 3-8 nm, the structure is uniform, the abundant nano-sheets are stacked into a three-dimensional structure, the number of active sites is effectively increased, the mass transfer process (diffusion of electrolyte and precipitation of gas) is improved, and the doping of Fe is beneficial to enhancing the conductivity of the catalyst, so that the transfer capability of electrons can be effectively improved, and the electrolytic water oxygen reaction is promoted.
2. The iron-modified nickel hydroxy sulfide ultrathin nanosheet array provided by the invention is used as a working electrode for hydrogen production by water electrolysis, shows excellent catalytic activity, and is 10,100 and 500mA cm under current density -2 At the time, the minimum required overpotential can be 221, 265 and 322mV, which is far lower than that of the pure nickel hydroxysulfide ultrathin nano-sheet array. Meanwhile, the catalyst can be used for preparing the catalyst at 10-500 mA cm -2 Is operated stably at a current density of (3).
Drawings
FIGS. 1 (a) and (b) are Scanning Electron Microscope (SEM) images of nickel hydroxysulfide (NiSOH) grown on nickel foam; (c) And (d) SEM image of iron-modified nickel hydroxysulfide (Fe-NiSOH for short).
FIG. 2 is a spectral contrast of NiSOH and Fe-NiSOH: (a) XRD and (b) Raman patterns.
Fig. 3 (a) - (c) Transmission Electron Microscope (TEM) images of Fe-NiSOH: (d) a Selected Area Electron Diffraction (SAED) pattern of Fe-NiSOH; (e) And (j) are distribution diagrams of corresponding elements of Fe-NiSOH respectively.
FIG. 4 is a graph of catalytic performance of NiSOH and Fe-NiSOH electrodes: (a) Linear Sweep Voltammetry (LSV) curve, (b) at 10,100 and 500mA cm -2 Overpotential at current density; (c) Tafel plot; (d) Electrochemical Impedance Spectroscopy (EIS).
FIG. 5 shows the Fe-NiSOH electrodes at 10,100 and 500mA cm -2 V-t curve for stable testing at current density of (c).
Detailed Description
Example 1
(1) Commercial nickel foam (2 cm. Times.1.5 cm) was sonicated with 3M HCl solution for 15min, in absolute ethanol for 5min, rinsed with deionized water for 1min, and dried for use.
(2) 1.369g (NH) 4 ) 2 S 2 O 8 Dissolve in a beaker of 80mL deionized water and stir for 10min followed by 0.496g Na 2 S 2 O 3 ·5H 2 O was dissolved in the above solution and stirred for 2min. And (3) placing the prepared solution in an ice water atmosphere, standing for 2min, and soaking the treated foam nickel in the solution for reaction for 5min. After the reaction is completed, washing the foam nickel with deionized water, and naturally airing to obtain the nickel hydroxysulfide ultrathin nanosheet array (expressed by NiSOH).
(3) For further introduction of Fe element, electrochemical anodic oxidation is used. Taking the nickel hydroxysulfide nano-sheet array prepared in the step (2) as a working electrode, wherein the effective area of the nickel hydroxysulfide nano-sheet array immersed in the electrolyte is 2cm 2 The counter electrode is a graphite rod electrode, and the Ag/AgCl electrode is used as the electrodeA reference electrode, electrolyte of 0.01M (NH 4 ) 2 Fe(SO 4 ) 2 Solution at 8mA cm -2 Is run for 20min at constant current density. After the reaction was completed, the nickel foam was removed and rinsed with deionized water for 2min. And (3) airing at room temperature to obtain the iron-modified nickel hydroxysulfide ultrathin nano-sheet array (expressed by Fe-NiSOH).
(4) The electrochemical performance of Fe-NiSOH was tested in a three electrode system, wherein Fe-NiSOH was used as the working electrode, hg/HgO electrode and graphite rod were used as the reference electrode, the counter electrode, respectively, and the electrolyte was a 1M KOH solution.
Fig. 1 (a) - (b) show SEM images of NiSOH with a large number of ultrathin nanoplatelets stacked in a nanoplatelet array. After electrochemical anodic oxidation, an iron-modified nickel hydroxysulfide ultrathin nanosheet array is obtained, the material is an amorphous iron-modified nickel hydroxysulfide nanosheet array on a growth bulk nickel substrate, the iron-modified nickel hydroxysulfide nanosheet array is formed by stacking iron-modified nickel hydroxysulfide ultrathin nanosheets, the thickness of the iron-modified nickel hydroxysulfide ultrathin nanosheets is 3-8 nm, as shown in fig. 1 (c) - (d), fe-NiSOH shows the nanosheet structure the same as that of NiSOH, and the Fe doping is not greatly destroyed to the morphology. In FIG. 2 (a), XRD spectra of Fe-NiSOH and NiSOH do not have distinct characteristic peaks, indicating that the catalyst prepared is an amorphous structure. The Raman spectrum of FIG. 2 (b) shows that NiSOH is at about 290 and 455cm -1 Two characteristic peaks are provided, which correspond to the vibration modes of Ni-S and Ni-O respectively. After doping with Fe element, ni-S characteristic peak due to Fe-NiSOH and 300cm -1 Together, exhibit a broader characteristic peak at 533 and 678cm -1 There is a new peak present corresponding to the fe—o vibrational mode of amorphous FeOOH. Thus, XRD and Raman spectra demonstrated successful synthesis of amorphous iron-modified nickel hydroxysulfide catalysts.
FIG. 3 (a) is a low-magnification TEM image of Fe-NiSOH, where a large number of ultrathin nanoplatelets overlap to form a three-dimensional nanostructure, which is advantageous for increasing the electrochemical specific surface area, thereby increasing the active sites for catalytic reactions. The high resolution TEM images of fig. 3 (b) and (c) did not find lattice fringes, demonstrating the amorphous structure of Fe-NiSOH, consistent with the XRD results. The electron selective diffraction (SAED) image in fig. 3 (d) also demonstrates the characteristics of its amorphous structure. In addition, the element distribution diagrams of fig. 3 (e) - (j) show that Ni, fe, O, S elements are equally distributed in the Fe-NiSOH ultrathin nanosheet array, wherein the Fe content is about 6.14%.
Fig. 4 is the results of an electrochemical performance test. FIGS. 4 (a) and (b) show linear scan curves of Fe-NiSOH and overpotential comparisons at corresponding current densities. After Fe is doped, the performance of Fe-NiSOH is obviously improved, and the Fe-NiSOH is in the range of 10,100 and 500mA cm -2 The overpotential at current densities was 221, 265 and 322mV, respectively, much lower than that required for pure NiSOH (299, 386, 470 mV). Furthermore, the Tafil slope of Fe-NiSOH was 44.61mV dec -1 Lower than pure NiSOH (86.22 mV dec -1 ) Indicating a faster OER reaction kinetics. The smaller charge transfer resistance also demonstrates that the incorporation of Fe increases the conductivity of the catalyst, favoring more efficient electron transfer and faster catalytic kinetics, thereby facilitating the progression of OER reactions. FIG. 5 is a plot of the stability test of Fe-NiSOH at different constant densities. As shown in the figure, the Fe-NiSOH electrode was at 10 and 100mA cm -2 Is stable for 100 hours at a current density and maintains performance without degradation. More importantly, the Fe-NiSOH is at 500mA cm -2 Is stable for 44 hours at the current density of (c).
Example 2
(1) Commercial nickel foam (2 cm. Times.3 cm) was sonicated with 3M HCl solution for 15min, in absolute ethanol for 5min, rinsed with deionized water for 1min, and dried for use.
(2) Will be 0.952g Na 2 S 2 O 8 Into a beaker of 80mL deionized water was stirred for 10min followed by 0.296g (NH) 4 ) 2 S 2 O 3 Dissolving in the above solution, and stirring for 2min. And (3) placing the prepared solution in an ice water atmosphere, standing for 2min, and soaking the treated foam nickel in the solution for reaction for 8min. After the reaction is completed, washing the foam nickel with deionized water, and naturally airing to obtain the nickel hydroxysulfide ultrathin nanosheet array.
(3) For further introduction of Fe element, electrochemical anodic oxidation is used. Taking the nickel hydroxysulfide nano-sheet array prepared in the step (2) as a working electrode, wherein the effective area of the nickel hydroxysulfide nano-sheet array immersed in the electrolyte is 3cm 2 The counter electrode is a graphite rod electrode, the Ag/AgCl electrode is used as a reference electrode, and the electrolyte is 0.005M (NH 4 ) 2 Fe(SO 4 ) 2 Solution at 8mA cm -2 Is run for 20min at constant current density. After the reaction was completed, the nickel foam was removed and rinsed with deionized water for 2min. And (3) airing at room temperature to obtain the iron-modified nickel hydroxy sulfide ultrathin nanosheet array.
(4) The electrochemical performance of Fe-NiSOH was tested in a three electrode system, wherein Fe-NiSOH was used as the working electrode, hg/HgO electrode and graphite rod were used as the reference electrode, the counter electrode, respectively, and the electrolyte was a 1M KOH solution. Fe-NiSOH at 10,100 and 500mA cm -2 The overpotential at the current density is listed in table 1.
Example 3
(1) Commercial nickel plates (2 cm. Times.4 cm) were sonicated with 3M HCl solution for 15min, in absolute ethanol for 5min, rinsed with deionized water for 1min, and dried for use.
(2) Will be 2.163g K 2 S 2 O 8 Into a beaker of 80mL deionized water was stirred for 10min followed by 0.296g (NH) 4 ) 2 S 2 O 3 Dissolving in the above solution, and stirring for 2min. And (3) placing the prepared solution in an ice water atmosphere, standing for 2min, and soaking the treated nickel sheet in the solution for reaction for 7min. After the reaction is completed, the nickel sheet is washed clean by deionized water, and the ultra-thin nickel hydroxysulfide nano sheet array is obtained after natural drying.
(3) For further introduction of Fe element, electrochemical anodic oxidation is used. Taking the nickel hydroxysulfide nano-sheet array prepared in the step (2) as a working electrode, wherein the effective area of the nickel hydroxysulfide nano-sheet array immersed in the electrolyte is 4cm 2 The counter electrode is a graphite rod electrode, the Ag/AgCl electrode is used as a reference electrode, and the electrolyte is 0.01M (NH 4 ) 2 Fe(SO 4 ) 2 Solution at 5mA cm -2 Is run at constant current density for 40min. ReactionAfter completion, the nickel plate was removed and rinsed with deionized water for 2min. And (3) airing at room temperature to obtain the iron-modified nickel hydroxy sulfide ultrathin nanosheet array.
(4) The electrochemical performance of Fe-NiSOH was tested in a three electrode system, wherein Fe-NiSOH was used as the working electrode, hg/HgO electrode and graphite rod were used as the reference electrode, the counter electrode, respectively, and the electrolyte was a 1M KOH solution. The current density was 10,100 and 500mA cm -2 The overpotential at that time is listed in table 1.
Example 4
(1) Ultrasonic treating commercial nickel screen (2 cm×3 cm) with 3M HCl solution for 15min, ultrasonic treating in absolute ethanol for 5min, washing with deionized water for 1min, and oven drying.
(2) 0.9128g (NH) 4 ) 2 S 2 O 8 Dissolve in a beaker of 80mL deionized water and stir for 10min, followed by 0.237g Na 2 S 2 O 3 ·5H 2 O was dissolved in the above solution and stirred for 2min. And (3) placing the prepared solution in an ice water atmosphere, standing for 2min, and soaking the treated nickel screen in the solution for reaction for 8min. After the reaction is completed, the nickel screen is washed clean by deionized water, and the nickel hydroxysulfide ultrathin nanosheet array is obtained after natural drying.
(3) For further introduction of Fe element, electrochemical anodic oxidation is used. Taking the nickel hydroxysulfide nano-sheet array prepared in the step (2) as a working electrode, wherein the effective area of the nickel hydroxysulfide nano-sheet array immersed in the electrolyte is 2cm 2 The counter electrode is a graphite rod electrode, the Ag/AgCl electrode is used as a reference electrode, and the electrolyte is 0.01M (NH 4 ) 2 Fe(SO 4 ) 2 Solution at 2mA cm -2 Is run at constant current density for 40min. After the reaction was completed, the nickel screen was removed and rinsed with deionized water for 2min. And (3) airing at room temperature to obtain the iron-modified nickel hydroxy sulfide ultrathin nanosheet array.
(4) The electrochemical performance of Fe-NiSOH was tested in a three electrode system, wherein Fe-NiSOH was used as the working electrode, hg/HgO electrode and graphite rod were used as the reference electrode, the counter electrode, respectively, and the electrolyte was a 1M KOH solution. The current density was 10,100 and 500mA cm -2 The overpotential at this time is listed in Table 1Is a kind of medium.
Example 5
(1) Commercial nickel foam (3 cm. Times.3 cm) was sonicated with 3M HCl solution for 15min, in absolute ethanol for 5min, rinsed with deionized water for 1min, and dried for use.
(2) 1.369g (NH) 4 ) 2 S 2 O 8 Dissolve in a beaker of 80mL deionized water and stir for 10min, followed by 0.541g K 2 S 2 O 3 ·5H 2 O was dissolved in the above solution and stirred for 2min. And (3) placing the prepared solution in an ice water atmosphere, standing for 2min, and soaking the treated foam nickel in the solution for reaction for 10min. After the reaction is completed, washing the foam nickel with deionized water, and naturally airing to obtain the nickel hydroxysulfide ultrathin nanosheet array.
(3) For further introduction of Fe element, electrochemical anodic oxidation is used. Taking the nickel hydroxysulfide nano-sheet array prepared in the step (2) as a working electrode, wherein the effective area of the nickel hydroxysulfide nano-sheet array immersed in the electrolyte is 4cm 2 The counter electrode is a graphite rod electrode, the Ag/AgCl electrode is used as a reference electrode, and the electrolyte is 0.015M (NH 4 ) 2 Fe(SO 4 ) 2 Solution at 10mA cm -2 Is run for 15min at constant current density. After the reaction was completed, the nickel foam was removed and rinsed with deionized water for 2min. And (3) airing at room temperature to obtain the iron-modified nickel hydroxy sulfide ultrathin nanosheet array.
(4) The electrochemical performance of Fe-NiSOH was tested in a three electrode system, wherein Fe-NiSOH was used as the working electrode, hg/HgO electrode and graphite rod were used as the reference electrode, the counter electrode, respectively, and the electrolyte was a 1M KOH solution. The current density was 10,100 and 500mA cm -2 The overpotential at that time is listed in table 1.
TABLE 1
Claims (9)
1. An iron modified nickel hydroxysulfide ultrathin nanosheet array is characterized in that: the material is an amorphous FeOOH modified nickel hydroxysulfide nano-sheet array grown on a bulk nickel substrate, and consists of self-supporting ultrathin amorphous nano-sheets, wherein the abundant nano-sheets are stacked into a three-dimensional structure, the thickness of the iron modified nickel hydroxysulfide nano-sheet is 3-8 nm, and the content of iron is 2.5-7.2% in terms of atomic percent.
2. The iron-modified ultra-thin nickel hydroxysulfide nanoplatelet array of claim 1, wherein: the iron-modified nickel hydroxy sulfide ultrathin nano-sheet array is prepared by a two-step oxidation method, wherein bulk nickel is used as a nickel source and a substrate, the nickel hydroxy sulfide ultrathin nano-sheet array is prepared by a wet chemical oxidation process, and the iron-modified nickel hydroxy sulfide ultrathin nano-sheet array is prepared by an anodic oxidation process.
3. The method for preparing the iron-modified nickel hydroxysulfide ultrathin nanosheet array of claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
step (1): immersing bulk nickel in a mixed solution of persulfate and thiosulfate for ice bath reaction to generate an ultra-thin nickel hydroxysulfide nano-sheet array;
step (2): the preparation method for preparing the iron-modified hydroxyl nickel sulfide ultrathin nanosheet array by electrochemical anodic oxidation comprises the following steps: and (3) taking the ultra-thin nickel hydroxysulfide nano-sheet array obtained in the step (1) as a working electrode, taking ferrous source substances as electrolytes, and performing electrochemical oxidation reaction to obtain the iron-modified ultra-thin nickel hydroxysulfide nano-sheet array.
4. A method of preparation according to claim 3, characterized in that: the bulk nickel of step (1) is any form of nickel; the persulfate is selected from (NH) 4 ) 2 S 2 O 8 ，Na 2 S 2 O 8 ，K 2 S 2 O 8 The method comprises the steps of carrying out a first treatment on the surface of the Thiosulfate is selected from Na 2 S 2 O 3 ，K 2 S 2 O 3 ，(NH 4 ) 2 S 2 O 3 。
5. A method of preparation according to claim 3, characterized in that: the concentration of the persulfate in the persulfate and thiosulfate solutions in the step (1) is 0.05-0.15 mol/L; the concentration of thiosulfate is 0.015-0.05 mol/L; the ice bath reaction time is 4-12 min.
6. A method of preparation according to claim 3, characterized in that: step (2) is to perform electrochemical oxidation reaction under constant positive current density of 1-12 mA cm -2 。
7. A method of preparation according to claim 3, characterized in that: in the step (2), the counter electrode is a graphite rod electrode, and the electrolyte is (NH) 4 ) 2 Fe(SO 4 ) 2 Solution, (NH) 4 ) 2 Fe(SO 4 ) 2 The concentration of the solution is 0.005-0.02 mol/L.
8. A method of preparation according to claim 3, characterized in that: the reaction time of the step (2) is 10-60 min.
9. The application of the iron-modified nickel hydroxysulfide ultrathin nanosheet array as an efficient and stable electrolytic water oxygen catalyst in oxidizing water, which comprises the following specific application methods: an iron-modified nickel hydroxysulfide ultrathin nanosheet array is used as an oxygen evolution electrode in an alkaline three-electrode system and is used for electrocatalytically oxidizing water.
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| CN106011911A (en) * | 2016-05-26 | 2016-10-12 | 重庆大学 | Method of partial vulcanization to improve oxygen evolution electrode performance of metal hydroxide |
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| CN110055557A (en) * | 2019-04-11 | 2019-07-26 | 中国科学院化学研究所 | A kind of three-dimensional nickel doped iron base oxygen-separating catalyst and its preparation method and application |
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| CN106011911A (en) * | 2016-05-26 | 2016-10-12 | 重庆大学 | Method of partial vulcanization to improve oxygen evolution electrode performance of metal hydroxide |
| CN108396329A (en) * | 2018-03-08 | 2018-08-14 | 北京化工大学 | A kind of two-phase nanometer nickel sulfide array material, the preparation method and the usage of Fe2O3 doping |
| CN110055557A (en) * | 2019-04-11 | 2019-07-26 | 中国科学院化学研究所 | A kind of three-dimensional nickel doped iron base oxygen-separating catalyst and its preparation method and application |
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