CN114561649A - Iron-modified hydroxyl nickel sulfide ultrathin nanosheet array, and preparation method and application thereof - Google Patents
Iron-modified hydroxyl nickel sulfide ultrathin nanosheet array, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114561649A CN114561649A CN202011361120.6A CN202011361120A CN114561649A CN 114561649 A CN114561649 A CN 114561649A CN 202011361120 A CN202011361120 A CN 202011361120A CN 114561649 A CN114561649 A CN 114561649A
- Authority
- CN
- China
- Prior art keywords
- nickel
- iron
- nanosheet array
- modified
- ultrathin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002135 nanosheet Substances 0.000 title claims abstract description 70
- BIBNGXLKRYORSJ-UHFFFAOYSA-M [Ni+]=S.[OH-] Chemical class [Ni+]=S.[OH-] BIBNGXLKRYORSJ-UHFFFAOYSA-M 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- KRIFFYDANHCLPO-UHFFFAOYSA-N nickel sulfanediol Chemical compound S(O)O.[Ni] KRIFFYDANHCLPO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 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
- 239000003792 electrolyte Substances 0.000 claims description 20
- GQDBBYLBYDPCTR-UHFFFAOYSA-N [Ni].O=S Chemical compound [Ni].O=S GQDBBYLBYDPCTR-UHFFFAOYSA-N 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 15
- 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 10
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910017472 S2O8 Inorganic materials 0.000 claims description 4
- 238000006056 electrooxidation reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 3
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 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
- 238000001035 drying Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000004098 selected area electron diffraction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910018553 Ni—O Inorganic materials 0.000 description 2
- 238000001237 Raman spectrum 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
- 238000013112 stability test Methods 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000004429 atom Chemical group 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
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002003 electron diffraction 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
- 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
- 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
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
Landscapes
- 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 sulfide hydroxy ultrathin nanosheet array, a preparation method and application thereof. The material is an amorphous iron-modified hydroxyl nickel sulfide nanosheet array growing on a bulk nickel substrate. The catalyst is prepared by a two-step oxidation method, the preparation method is simple and efficient, and the doping of iron is beneficial to improving the conductivity of the catalyst and improving the transfer capability of electrons, so that the electrolytic water Oxygen Evolution Reaction (OER) is promoted. The catalyst exhibits excellent OER catalytic activity at current densities of 10,100 and 500mA cm‑2The minimum required overpotential can be 221, 265 and 322mV, which is far lower than that of a pure nickel hydroxy sulfide ultrathin nanosheet array. At the same time, the catalystCan be 10-500 mA cm‑2Stable operation at a current density of (d).
Description
Technical Field
The invention relates to the technical field of oxygen catalysts for electrolysis of water, in particular to an iron-modified nickel sulfide hydroxy ultrathin nanosheet array, a preparation method and application thereof.
Background
Due to the advantages of high energy density of hydrogen and friendly products, hydrogen production by water electrolysis becomes one of the leading scientific methods for solving the problems of energy and environment. Electrolyzed water consists of two half-reactions, the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER), respectively. In both half-reactions, the OER at the anode becomes the major bottleneck limiting hydrogen production from water electrolysis due to slow kinetics. Although Ru/Ir-based catalysts exhibit very good OER activity, their large-scale application is hampered by scarce resources, high cost and poor stability at high current densities. Therefore, the development of efficient, low-cost catalysts from the earth's abundant resources is imminent.
Among the previously reported catalysts, transition metal hydroxides are of great interest for their low cost, unique crystal structure and effective OER activity, but their limited specific surface area and poor intrinsic conductivity result in inefficient transport of electrons, resulting in excessively high overpotentials and thus consumption of large amounts of electrical energy. Effective strategies are used to improve the OER activity of these catalysts, such as preparing special nanostructures to increase the number of catalytically active sites, doping heterogeneous atoms to effectively improve the intrinsic activity of the catalyst. On the basis, the derived S-doped metal hydroxide or hydroxyl metal sulfide (such as NiSOH and the like) has a good catalytic effect. Wherein, the sulfur atom can not only adjust the electronic structure of the metal, but also influence the adsorption strength of the intermediate active substance on the active site, thereby being beneficial to adsorption and desorption (adv.Mater.2018,30,1800757; nat.Commun.2020,11,5075). However, the nickel hydroxysulfide reported at present still has the problems of high overpotential, poor stability and the like, and the cost is further increased due to the complex preparation process, high energy consumption and the like. Therefore, if a simple preparation method can be developed to modify nickel hydroxysulfide, not only can the OER activity of the catalyst be effectively improved, but also the cost can be reduced, and the commercialization of the catalyst can be accelerated.
Disclosure of Invention
In order to solve the problems, the invention aims to invent an efficient OER catalyst and a simple preparation method thereof, and particularly relates to an iron-modified nickel hydroxysulfide ultrathin nanosheet array and a preparation method thereof.
An iron-modified nickel hydroxy sulfide ultrathin nanosheet array is an amorphous iron-modified nickel hydroxy sulfide nanosheet array growing on a bulk nickel substrate.
According to the scheme, the thickness of the iron-modified nickel hydroxy sulfide nanosheet in the iron-modified nickel hydroxy sulfide ultrathin nanosheet array is 3-8 nm, and the iron content is 2.5-7.2% (atomic percent).
According to the scheme, the iron-modified nickel oxysulfide ultrathin nanosheet array is prepared by a two-step oxidation method, firstly, bulk nickel is used as a nickel source and a substrate, a nickel oxysulfide ultrathin nanosheet array is prepared through a wet chemical oxidation process, and secondly, the iron-modified nickel oxysulfide ultrathin nanosheet array is prepared through an anodic oxidation process.
The preparation method of the iron-modified nickel oxysulfide ultrathin nanosheet array comprises the following steps:
step (1): soaking the block nickel in persulfate and thiosulfate solution for ice-bath reaction to obtain a nickel hydroxysulfide ultrathin nanosheet array;
step (2): preparing an iron-modified nickel oxysulfide ultrathin nanosheet array by electrochemical anodic oxidation, wherein the preparation steps are as follows: and (2) carrying out electrochemical oxidation reaction by taking the hydroxy nickel sulfide ultrathin nanosheet array obtained in the step (1) as a working electrode and taking a ferrous iron source substance as electrolyte to obtain an iron-modified hydroxy nickel sulfide ultrathin nanosheet array.
According to the scheme, the bulk nickel can be any form of nickel, such as foam nickel, nickel sheets, nickel nets and other macroscopic forms of bulk nickel.
According to the above scheme, the persulfate is selected from (NH)4)2S2O8，Na2S2O8，K2S2O8(ii) a The thiosulfate is selected from Na2S2O3，K2S2O3，(NH4)2S2O3。
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 the 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 the persulfate and the thiosulfate is subjected to precooling treatment in an ice bath.
According to the scheme, the persulfate is added with the deionized water to prepare the solution, and then the thiosulfate is added and stirred to obtain the persulfate-thiosulfate mixed solution.
According to the scheme, after the reaction in the step (1) is finished, the nickel block is washed clean by deionized water, and the nickel hydroxysulfide ultrathin nanosheet array is obtained after natural airing.
According to the scheme, the ice-bath reaction time in the step (1) is 4-12 min.
According to the scheme, the step (2) is to carry out electrochemical oxidation reaction under constant positive current density.
According to the scheme, the constant current density of the step (2) 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)2Fe(SO4)2And (3) solution. And after the reaction is finished, washing with deionized water, and airing at room temperature to obtain the iron-modified nickel oxysulfide ultrathin nanosheet array.
According to the scheme, (NH) in the step (2)4)2Fe(SO4)2The 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 oxysulfide ultrathin nanosheet array as an efficient and stable oxygen generation catalyst for electrolyzed water in oxidized water comprises the following specific application methods: the iron-modified nickel sulfide hydroxyl ultrathin nanosheet array is used as an oxygen evolution electrode in an alkaline three-electrode system and is used for electrocatalytic oxidation of water.
The invention has the beneficial effects that:
1. the invention originally develops a simple two-step oxidation preparation method for the first time. Firstly, preparing a hydroxyl nickel sulfide ultrathin nanosheet array by a wet chemical oxidation method, and finally obtaining an amorphous iron-modified hydroxyl nickel sulfide ultrathin nanosheet array by an anodic oxidation method. The catalyst is composed of self-supporting ultrathin amorphous nanosheets, the ultrathin nanosheets are 3-8 nm in thickness and uniform in structure, rich nanosheets 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, the doping of Fe is beneficial to enhancing the conductivity of the catalyst, the transfer capability of electrons can be effectively improved, and the oxygen production reaction of electrolyzed water is promoted.
2. The iron-modified nickel oxysulfide ultrathin nanosheet array provided by the invention is used as a working electrode for hydrogen production by water electrolysis, shows excellent catalytic activity and has current densities of 10,100 and 500mA cm-2The minimum required overpotential can be 221, 265 and 322mV, which is far lower than that of a pure nickel hydroxysulfide ultrathin nanosheet array. Meanwhile, the catalyst can be in the range of 10-500 mA cm-2Stable operation at a current density of (a).
Drawings
FIGS. 1(a) and (b) are Scanning Electron Microscope (SEM) images of nickel hydroxysulfide (NiSOH for short) grown on nickel foam; (c) and (d) SEM images of iron-modified nickel hydroxysulfide (Fe-NiSOH for short).
FIG. 2 is a line comparison of NiSOH and Fe-NiSOH: (a) XRD and (b) Raman pattern.
FIG. 3(a) to (c) Transmission Electron Microscope (TEM) images of Fe-NiSOH: (d) a Selected Area Electron Diffraction (SAED) pattern for Fe-NiSOH; (e) each of (j) to (j) is a distribution diagram of the corresponding element of Fe-NiSOH.
FIG. 4 is a graph of the catalytic performance of NiSOH and Fe-NiSOH electrodes: (a) linear Sweep Voltammogram (LSV) curves, (b) at 10,100 and 500mA cm-2An overpotential at current density; (c) tafel (Tafel) diagram; (d) electrochemical Impedance Spectroscopy (EIS).
FIG. 5 shows Fe-NiSOH electrodes at 10,100 and 500mA cm-2The v-t curve of the stability test at the current density of (1).
Detailed Description
Example 1
(1) Commercial nickel foam (2cm multiplied by 1.5cm) is treated by ultrasonic treatment for 15min by using 3M HCl solution, treated by ultrasonic treatment for 5min in absolute ethyl alcohol and washed by deionized water for 1min, and then dried for later use.
(2) 1.369g(NH4)2S2O8Dissolve in a beaker of 80mL deionized water and stir for 10min, then add 0.496g Na2S2O3·5H2Dissolving O in the solution, and stirring for 2 min. And (3) standing the prepared solution in an ice water atmosphere for 2min, and soaking the treated foam nickel in the solution for reacting for 5 min. And after the reaction is finished, washing the foam nickel by using deionized water, and naturally airing to obtain the nickel oxysulfide ultrathin nanosheet array (represented by NiSOH).
(3) In order to further introduce the Fe element, an electrochemical anode oxidation method is adopted. Taking the hydroxyl nickel sulfide nanosheet array prepared in the step (2) as a working electrode, and immersing the working electrode into an electrolyte with an effective area of 2cm2The 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)2Fe(SO4)2Solution at 8mA cm-2Was run for 20min at constant current density. After the reaction was complete, the nickel foam was removed and rinsed with deionized water for 2 min. And (4) drying at room temperature to obtain the iron-modified nickel oxysulfide ultrathin nanosheet array (expressed by Fe-NiSOH).
(4) The electrochemical performance of Fe-NiSOH was tested in a three-electrode system, in which Fe-NiSOH was used as the working electrode, Hg/HgO electrode and graphite rod were used as the reference electrode and counter electrode, respectively, and the electrolyte was 1M KOH solution.
Fig. 1(a) - (b) show SEM images of NiSOH with a large number of ultrathin nanosheets stacked into a nanosheet array. The iron-modified nickel hydroxysulfide ultrathin nanosheet array is obtained after electrochemical anodic oxidation, the material is an amorphous iron-modified nickel hydroxysulfide nanosheet array on a growth block 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, and as shown in fig. 1(c) - (d), Fe-NiSOH shows a nanosheet structure the same as NiSOH, which indicates that the doping of Fe does not cause great damage to the morphology. In FIG. 2(a), the XRD lines of Fe-NiSOH and NiSOH do not have distinct characteristic peaks, indicating that the catalyst prepared is an amorphous structure. Drawing of FIG. 2(b)The Raman spectra showed that NiSOH was between about 290 and 455cm-1Has two characteristic peaks corresponding to the vibration modes of Ni-S and Ni-O respectively. After the Fe element is doped, the characteristic peak of Ni-S is 300cm-1The characteristic peaks of Ni-O are combined together, and the wider characteristic peaks are displayed at 533 cm and 678cm-1There appears a new peak corresponding to the Fe-O vibrational mode of amorphous FeOOH. Thus, XRD and Raman spectra demonstrate the successful synthesis of amorphous iron-modified nickel hydroxy sulfide catalysts.
FIG. 3(a) is a low-magnification TEM image of Fe-NiSOH, and a large number of ultrathin nanosheets are overlapped to form a three-dimensional nanostructure, which is beneficial to improving the electrochemical specific surface area, so that the active sites of catalytic reaction are increased. The high resolution TEM images of FIGS. 3(b) and (c) did not reveal lattice fringes, demonstrating the amorphous structure of Fe-NiSOH, consistent with the results obtained by XRD. The selective electron diffraction (SAED) image in fig. 3(d) also demonstrates the amorphous structure. In addition, the element distribution diagrams of fig. 3(e) - (j) show that the elements of Ni, Fe, O and S are uniformly distributed in the Fe-NiSOH ultrathin nanosheet array, wherein the content of Fe is about 6.14%.
Fig. 4 shows the results of electrochemical performance tests. FIGS. 4(a) and (b) show the linear scan curves for Fe-NiSOH and the overpotential contrast at the corresponding current densities. After Fe is doped, the performance of Fe-NiSOH is obviously improved at 10,100 and 500mA cm-2The overpotentials at current densities were 221, 265, and 322mV, respectively, which are much lower than the overpotentials (299, 386, 470mV) required for pure NiSOH. In addition, the Tafel slope for Fe-NiSOH was 44.61mV dec-1Lower than pure NiSOH (86.22mV dec)-1) Illustrating its more rapid OER reaction kinetics. The smaller charge transfer resistance also indicates that the incorporation of Fe increases the conductivity of the catalyst, favoring more efficient electron transfer and faster catalytic kinetics, thus facilitating the OER reaction. FIG. 5 is a stability test curve of Fe-NiSOH at different constant densities. As shown, the Fe-NiSOH electrodes were at 10 and 100mA cm-2Stable operation for 100 hours at the current density of (1) and no performance degradation. More importantly, Fe-NiSOH is 500mA cm-2At a current density ofCan be kept stable for 44 hours.
Example 2
(1) Commercial nickel foam (2cm multiplied by 3cm) is treated by ultrasonic treatment for 15min by using 3M HCl solution, treated by ultrasonic treatment for 5min in absolute ethyl alcohol and washed by deionized water for 1min, and then dried for later use.
(2) Mixing 0.952g of Na2S2O8Dissolve in a beaker of 80mL deionized water and stir for 10min, then add 0.296g (NH)4)2S2O3Dissolving in the above solution, and stirring for 2 min. And (3) standing the prepared solution in an ice water atmosphere for 2min, and soaking the treated foam nickel in the solution to react for 8 min. And after the reaction is finished, washing the foam nickel with deionized water, and naturally airing to obtain the hydroxy nickel sulfide ultrathin nanosheet array.
(3) In order to further introduce the Fe element, an electrochemical anode oxidation method is adopted. Taking the hydroxyl nickel sulfide nanosheet array prepared in the step (2) as a working electrode, and immersing the working electrode into electrolyte with an effective area of 3cm2The 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)2Fe(SO4)2Solution at 8mA cm-2Was run for 20min at constant current density. After the reaction was complete, the nickel foam was removed and rinsed with deionized water for 2 min. And drying at room temperature to obtain the iron-modified nickel oxysulfide ultrathin nanosheet array.
(4) The electrochemical performance of Fe-NiSOH was tested in a three-electrode system, in which Fe-NiSOH was used as the working electrode, Hg/HgO electrode and graphite rod were used as the reference electrode and counter electrode, respectively, and the electrolyte was 1M KOH solution. Fe-NiSOH at 10,100 and 500mA cm-2The overpotentials at current densities of (a) are listed in table 1.
Example 3
(1) A commercial nickel sheet (2cm multiplied by 4cm) is subjected to ultrasonic treatment for 15min by using a 3M HCl solution, ultrasonic treatment for 5min in absolute ethyl alcohol and washing for 1min by using deionized water, and then the nickel sheet is dried for later use.
(2) 2.163g K2S2O8Dissolve in a beaker of 80mL deionized water and stir for 10min, then add 0.296g (NH)4)2S2O3Dissolving in the above solution, and stirring for 2 min. And (3) standing the prepared solution in an ice water atmosphere for 2min, and soaking the treated nickel sheet in the solution to react for 7 min. And after the reaction is finished, washing the nickel plate with deionized water, and naturally airing to obtain the hydroxy nickel sulfide ultrathin nanosheet array.
(3) In order to further introduce the Fe element, an electrochemical anode oxidation method is adopted. Taking the hydroxyl nickel sulfide nanosheet array prepared in the step (2) as a working electrode, and immersing the working electrode into an electrolyte with an effective area of 4cm2The 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)2Fe(SO4)2Solution at 5mA cm-2Was run for 40min at constant current density. After the reaction was complete, the nickel plate was removed and rinsed with deionized water for 2 min. And (3) airing at room temperature to obtain the iron-modified nickel sulfide hydroxy ultrathin nanosheet array.
(4) The electrochemical performance of Fe-NiSOH was tested in a three-electrode system, in which Fe-NiSOH was used as the working electrode, Hg/HgO electrode and graphite rod were used as the reference electrode and counter electrode, respectively, and the electrolyte was 1M KOH solution. The current densities were 10,100 and 500mA cm-2The overpotentials in time are listed in table 1.
Example 4
(1) Carrying out ultrasonic treatment on a commercial nickel screen (2cm multiplied by 3cm) by using a 3M HCl solution for 15min, carrying out ultrasonic treatment in absolute ethyl alcohol for 5min, washing by using deionized water for 1min, and drying for later use.
(2) 0.9128g (NH)4)2S2O8Dissolved in a beaker of 80mL deionized water and stirred for 10min, followed by 0.237g Na2S2O3·5H2Dissolving O in the solution, and stirring for 2 min. And (3) standing the prepared solution in an ice water atmosphere for 2min, and soaking the treated nickel screen in the solution to react for 8 min. And after the reaction is finished, washing the nickel screen clean by using deionized water, and naturally airing to obtain the hydroxy nickel sulfide ultrathin nanosheet array.
(3) In order to further introduce the Fe element, an electrochemical anode oxidation method is adopted. Preparing in step (2)The obtained hydroxyl nickel sulfide nanosheet array is used as a working electrode, and the effective area of the working electrode immersed in electrolyte is 2cm2The 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)2Fe(SO4)2Solution at 2mA cm-2Was run for 40min at constant current density. After the reaction was complete, the nickel screen was removed and rinsed with deionized water for 2 min. And (3) airing at room temperature to obtain the iron-modified nickel sulfide hydroxy ultrathin nanosheet array.
(4) The electrochemical performance of Fe-NiSOH was tested in a three-electrode system, in which Fe-NiSOH was used as the working electrode, Hg/HgO electrode and graphite rod were used as the reference electrode and counter electrode, respectively, and the electrolyte was 1M KOH solution. The current densities were 10,100 and 500mA cm-2The overpotentials in time are listed in table 1.
Example 5
(1) Commercial nickel foam (3cm multiplied by 3cm) is treated by ultrasonic treatment for 15min by using 3M HCl solution, treated by ultrasonic treatment for 5min in absolute ethyl alcohol and washed by deionized water for 1min, and then dried for later use.
(2) 1.369g (NH)4)2S2O8Dissolve in 80mL deionized water beaker and stir for 10min, then mix 0.541g K2S2O3·5H2Dissolving O in the solution, and stirring for 2 min. And (3) standing the prepared solution in an ice water atmosphere for 2min, and soaking the treated foam nickel in the solution for reaction for 10 min. And after the reaction is finished, washing the foam nickel with deionized water, and naturally airing to obtain the hydroxy nickel sulfide ultrathin nanosheet array.
(3) In order to further introduce the Fe element, an electrochemical anode oxidation method is adopted. Taking the hydroxyl nickel sulfide nanosheet array prepared in the step (2) as a working electrode, and immersing the working electrode into an electrolyte with an effective area of 4cm2The 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)2Fe(SO4)2Solution at 10mA cm-2Was run for 15min at constant current density. After the reaction was complete, the nickel foam was removed and rinsed with deionized water for 2 min. Drying at room temperature to obtain the iron repairingDecorated ultra-thin nanosheet arrays of nickel hydroxysulfide.
(4) The electrochemical performance of Fe-NiSOH was tested in a three-electrode system, in which Fe-NiSOH was used as the working electrode, Hg/HgO electrode and graphite rod were used as the reference electrode and counter electrode, respectively, and the electrolyte was 1M KOH solution. The current densities were 10,100 and 500mA cm-2The overpotentials in time are listed in table 1.
TABLE 1
Claims (10)
1. An iron-modified hydroxyl nickel sulfide ultrathin nanosheet array is characterized in that: the material is an amorphous iron-modified hydroxyl nickel sulfide nanosheet array growing on a bulk nickel substrate.
2. The iron-modified ultrathin nickel oxysulfide nanosheet array of claim 1, wherein: the thickness of the iron-modified nickel hydroxy sulfide nanosheet is 3-8 nm, and the iron content is 2.5-7.2% (atomic percent).
3. The iron-modified ultrathin nickel oxysulfide nanosheet array of claim 1, wherein: the iron-modified nickel oxysulfide ultrathin nanosheet array is prepared by a two-step oxidation method, and the iron-modified nickel oxysulfide ultrathin nanosheet array is prepared by firstly taking bulk nickel as a nickel source and a substrate through a wet chemical oxidation process and then carrying out an anodic oxidation process on the nickel oxysulfide ultrathin nanosheet array.
4. The preparation method of the iron-modified nickel sulfide hydroxy ultrathin nanosheet array is characterized by comprising the following steps of: the method comprises the following steps:
step (1): soaking the block nickel in a mixed solution of persulfate and thiosulfate for ice-bath reaction to generate a hydroxyl nickel sulfide ultrathin nanosheet array;
step (2): preparing an iron-modified nickel oxysulfide ultrathin nanosheet array by electrochemical anodic oxidation, wherein the preparation steps are as follows: and (2) performing electrochemical oxidation reaction by taking the hydroxy nickel sulfide ultrathin nanosheet array obtained in the step (1) as a working electrode and a ferrous iron source substance as an electrolyte to obtain an iron-modified hydroxy nickel sulfide ultrathin nanosheet array.
5. The method of claim 4, wherein: the bulk nickel in the step (1) is any form of nickel, such as macroscopic forms of foam nickel, nickel sheets, nickel nets and the like; the persulfate is selected from (NH)4)2S2O8，Na2S2O8，K2S2O8(ii) a The thiosulfate is selected from Na2S2O3，K2S2O3，(NH4)2S2O3。
6. The method of claim 4, wherein: the concentration of the persulfate in the persulfate and thiosulfate solution in the step (1) is 0.05-0.15 mol/L; the concentration of the thiosulfate is 0.015-0.05 mol/L; the ice-bath reaction time is 4-12 min.
7. The method of manufacturing according to claim 4, characterized in that: the step (2) is to carry out electrochemical oxidation reaction under constant positive current density, wherein the constant current density is 1-12 mA cm-2。
8. The method of claim 4, wherein: in the step (2), the counter electrode is a graphite rod electrode, and the electrolyte is (NH)4)2Fe(SO4)2Solution, (NH)4)2Fe(SO4)2The concentration of the solution is 0.005-0.02 mol/L.
9. The method of manufacturing according to claim 4, characterized in that: the reaction time of the step (2) is 10-60 min.
10. The application of the iron-modified nickel oxysulfide ultrathin nanosheet array as an efficient and stable oxygen generation catalyst for electrolysis water in oxidizing water is as follows: the iron-modified hydroxyl nickel sulfide ultrathin nanosheet array is used as an oxygen evolution electrode in an alkaline three-electrode system and is used for electrocatalytic oxidation of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011361120.6A CN114561649B (en) | 2020-11-27 | 2020-11-27 | Iron-modified nickel hydroxy sulfide ultrathin nanosheet array, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011361120.6A CN114561649B (en) | 2020-11-27 | 2020-11-27 | Iron-modified nickel hydroxy sulfide ultrathin nanosheet array, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114561649A true CN114561649A (en) | 2022-05-31 |
| CN114561649B CN114561649B (en) | 2023-11-03 |
Family
ID=81712554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011361120.6A Active CN114561649B (en) | 2020-11-27 | 2020-11-27 | Iron-modified nickel hydroxy sulfide ultrathin nanosheet array, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114561649B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110479281A (en) * | 2019-08-12 | 2019-11-22 | 广西师范大学 | One kind being based on FeOOH-NiOOH/NF elctro-catalyst and preparation method |
-
2020
- 2020-11-27 CN CN202011361120.6A patent/CN114561649B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110479281A (en) * | 2019-08-12 | 2019-11-22 | 广西师范大学 | One kind being based on FeOOH-NiOOH/NF elctro-catalyst and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| CHUQIANG HUANG ET AL.: "Rapid self-reconstruction of Fe-modified Ni hydroxysulfide for efficient and stable large-current-density water/seawater oxidation", 《ENERGY ENVIRON. SCI》, vol. 15, pages 4647 - 4658 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114561649B (en) | 2023-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110639534B (en) | Oxygen evolution electrocatalytic material and preparation method and application thereof | |
| CN112626540B (en) | Multi-stage structure electrode for water electrolysis and preparation method thereof | |
| CN110699702B (en) | Hillock-shaped in-situ nickel-vanadium double metal hydroxide catalyst and preparation method and application thereof | |
| CN112791736A (en) | WP2/Cu3Application of P composite nano-structure catalyst in aspect of hydrogen production by electrolyzing water | |
| CN109860634B (en) | Method for manufacturing manganese cobalt oxide and nitrogen-doped carbon in-situ composite electrode | |
| CN112575348B (en) | NF-NiFeOx(OH)y-S electrode, its preparation and application as OER catalytic material | |
| CN113279005A (en) | Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution | |
| CN110629248A (en) | Fe-doped Ni (OH)2Preparation method of/Ni-BDC electrocatalyst | |
| CN112921351B (en) | Preparation method and application of self-supporting catalytic electrode | |
| CN113789545A (en) | Water electrolysis catalyst and preparation method and application thereof | |
| CN110368961B (en) | Preparation method of lamellar self-assembly starfish-shaped nickel-rich nickel telluride catalyst | |
| CN113293407B (en) | Iron-rich nanobelt oxygen evolution electrocatalyst and preparation method thereof | |
| CN115466980A (en) | Electrode using foam nickel loaded nickel sulfide as urea oxidation catalyst and preparation method thereof | |
| CN114561649B (en) | Iron-modified nickel hydroxy sulfide ultrathin nanosheet array, preparation method and application thereof | |
| CN110129814B (en) | Electrocatalytic electrode with ditungsten carbide inverse opal composite micro-nano structure and preparation and hydrogen evolution application thereof | |
| CN118256951B (en) | Iridium monoatomic @ oxygen-enriched vacancy nickel hydroxide nano-sheet and preparation method and application thereof | |
| CN117446920B (en) | Two-dimensional nano-sheet heterojunction electrocatalyst and preparation method and application thereof | |
| CN115896845B (en) | Preparation method of self-supporting zinc-doped nickel/iron oxyhydroxide catalytic electrode | |
| CN111774071B (en) | Ternary metal sulfide nanosheet material, preparation method thereof and application of ternary metal sulfide nanosheet material in water electrolysis | |
| CN113026049B (en) | Two-step solvothermal method for preparing NiFe (CN)5NO-Ni3S2-NF composite catalyst and application thereof | |
| CN115505956A (en) | Method for preparing Ru and Al co-doped NiFe-OH hydrogen evolution electrocatalyst based on corrosion engineering and application thereof | |
| CN118531432A (en) | Directional growth sulfur-nickel-iron oxyhydroxide composite material, preparation method and application thereof | |
| CN117604568A (en) | Fe-LDH@Co 3 (PO 4)2 ·4H 2 Preparation method and application of O/NF catalyst | |
| CN116926591A (en) | Heterogeneous composite electrode material and preparation method and application thereof | |
| CN116752186A (en) | RhNi composite electrocatalyst for electrocatalytic hydrogen evolution and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |