CN112899723A - Metal organic framework derived iron-nickel metal sulfide catalyst, preparation and application thereof - Google Patents
Metal organic framework derived iron-nickel metal sulfide catalyst, preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000004729 solvothermal method Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052683 pyrite Inorganic materials 0.000 claims description 3
- 239000011028 pyrite Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 239000012456 homogeneous solution Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005486 sulfidation Methods 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000004832 voltammetry Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- -1 iron metals Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
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Abstract
金属有机框架衍生的铁镍金属硫化物催化剂及制备与应用，涉及可再生能源催化材料。通过简易的溶剂热硫化得到的铁镍金属硫化物催化剂，对于电催化析氧反应表现出较好的活性。制备方法包括如下步骤：取硫代乙酰胺溶于乙醇，然后加入MIL‑88，搅拌一定时间后，转移至反应釜中进行溶剂热反应；溶剂热处理后，依次经过冷却，洗涤，干燥即得到所述催化剂。其结构内部的硫化物种能够增强导电性，并且可以原位生成羟基氧化物种，暴露更多的活性位点，富含介孔的孔道结构有利于快速的电子传输以及水分子吸附和气体产物的释放，提升电催化活性。该电催化剂具有催化活性高、稳定性好，制备工艺简便的优点，具有较强的应用价值。
Metal-organic framework-derived iron-nickel metal sulfide catalyst, preparation and application, involving renewable energy catalytic materials. The iron-nickel metal sulfide catalyst obtained by simple solvothermal sulfidation showed good activity for electrocatalytic oxygen evolution reaction. The preparation method includes the following steps: dissolving thioacetamide in ethanol, then adding MIL-88, stirring for a certain period of time, and then transferring to a reaction kettle for solvothermal reaction; after solvothermal treatment, sequentially cooling, washing, and drying to obtain the obtained product. described catalyst. The sulfide species inside its structure can enhance electrical conductivity, and can generate oxyhydroxide species in situ, exposing more active sites, and the mesoporous-rich pore structure is conducive to fast electron transport as well as water molecule adsorption and gas product release. , to enhance the electrocatalytic activity. The electrocatalyst has the advantages of high catalytic activity, good stability and simple preparation process, and has strong application value.
Description
Technical Field
The invention relates to a renewable energy catalytic material, in particular to an iron-nickel metal sulfide catalyst derived from a metal organic framework, and preparation and application thereof.
Background
Hydrogen energy is a secondary energy source which attracts attention, and has the characteristics of safety, environmental protection, high energy and cleanness, so that it is widely used in the fields of power generation, power automobiles, fuel cells, and the like. The hydrogen energy technology is listed as energy in the fifteen-year plan of scientific and technological development and 2015-year long-term planning in ChinaIn the source field, this means the important position of hydrogen energy in the strategy of energy development. The hydrogen production technology by water electrolysis is a way for efficiently preparing high-purity hydrogen energy, and the core of the technology is Oxygen Evolution Reaction (OER) of an anode and Hydrogen Evolution Reaction (HER) of a cathode. Wherein, the oxygen evolution reaction is a multi-step proton coupling electron transfer process with higher energy barrier, so the whole water decomposition reaction is limited to proceed. At present, the commercial catalysts are mostly noble metal catalysts with high price, such as IrO2And RuO2In order to reduce the preparation cost of the catalyst and improve the catalytic activity, it is necessary to research an efficient and cheap electrocatalyst for accelerating the OER reaction.
Of the many non-noble metal electrocatalysts, the metal-organic framework catalysts attract attention of researchers due to their large specific surface area, highly dispersed metal centers, and diversified organic ligands. For example, chinese patent CN111921560A discloses a preparation method of an ultrathin Metal Organic Framework (MOF) nanosheet catalyst and a study on oxygen evolution performance, in which ferrocenecarboxylic acid and terephthalic acid are dissolved in a mixed solution of N, N-dimethylformamide, ethanol and water, followed by introduction of a cobalt salt and an acid-binding agent, followed by ultrasonic stripping, and then by centrifugal washing, a nanosheet catalyst is obtained. The metal organic framework nanosheet is improved due to lattice distortion and large specific surface area activity. Xie et al (M.Xie, Y.Ma, D.Lin, C.xu, F.Xie, W.Zeng, Nanoscale2020,12,67-71) report that a MIL-53(Co-Fe) catalyst is applied to the research of oxygen evolution reaction, and the metal organic framework improves the electrocatalytic activity through the synergistic effect of cobalt and iron metals and the characteristic of sheet morphology. Li et al (F. -L.Li, Q.Shao, X.Huang, J. -P.Lang, Angew.chem.int.Ed.Engl.2018,57, 1888-. However, the existence of the organic ligand in the metal organic framework leads to poor conductivity of the material and limits the occurrence of oxygen evolution reaction.
Transition metal sulfides are widely studied in the field of electrocatalysis because of their high electrical conductivity. For example, chinese patent CN111774071A discloses a method for preparing ternary metal sulfide nanosheet material, which comprises adding foamed metal (Ni, Cu, Ti, Al, Co, Zn), ferric chloride and sodium sulfide into an aqueous solution, and heating in one pot to obtain ternary metal sulfide nanosheet. The ultrathin morphology of the material has a larger specific surface area, promotes rapid mass transfer and electron transmission, reduces the density of active center electron cloud by doping heteroatom, reduces the adsorption free energy of the intermediate, and promotes the oxygen evolution reaction. Chinese patent CN112023946A discloses a layered nickel-iron double hydroxide sulfide catalyst synthesized by hydrothermal sulfidation. The catalyst improves the catalytic activity and the electrical conductivity of the nickel-iron layered double hydroxide by doping sulfur, and is beneficial to the transfer of electrons.
At present, the research on the electronic and structural coordinated regulation of metal organic framework materials to obtain a derivative catalyst for oxygen evolution reaction is only reported, and Huang et al (Z.Q.Huang, B.Wang, D.S.Pan, L.L.Zhou, Z.H.Guo, J.L.Song, ChemSusChem 2020,13, 2564-one 2570.) report the oxygen evolution reaction electrocatalyst of nitrogen-sulfur doped cobalt MOF iron base. And doping the modified pore channel structure with hetero atoms to promote mass and charge transmission. The Chinese patent CN109908963A obtains the Ni-BDC @ NiS nano array by vulcanizing Ni-BDC, compounds a high-conductivity sulfide material and retains the form of MOF, thereby improving the activity of OER. However, the preparation method of the iron-nickel metal sulfide catalyst derived from the metal organic framework is researched based on the defects of poor performance, high cost, complicated preparation process and the like of the metal organic framework derived catalyst, so that the preparation method has great significance for obtaining the oxygen evolution reaction catalyst which has low over potential, high stability, low price and easiness in preparation.
Disclosure of Invention
The first purpose of the present invention is to overcome the above drawbacks of the prior art, and to provide an iron-nickel metal sulfide catalyst which is favorable for adsorption of water molecules and precipitation of oxygen during the reaction process, promotes the oxygen evolution reaction, has excellent electrochemical performance, and is derived from a metal organic framework.
The second purpose of the invention is to provide a preparation method of the iron-nickel metal sulfide catalyst, which has low cost, abundant raw materials and simple preparation process.
The third purpose of the invention is to provide the application of the iron-nickel metal sulfide catalyst in the oxygen evolution reaction of electrolyzed water.
The iron-nickel metal sulfide catalyst mainly comprises iron-nickel bimetallic sulfide in a pyrite crystal form, wherein the mass content of iron in the catalyst is 10-30%, the mass content of nickel is 1-10%, and the mass content of sulfur is about 5-30%.
The preparation method of the iron-nickel metal sulfide catalyst comprises the following steps:
1) weighing iron salt, nickel salt and terephthalic acid, dissolving in N, N-dimethylformamide, and stirring to form a uniform solution;
2) measuring a sodium hydroxide solution, adding the sodium hydroxide solution into the solution obtained in the step 1), and uniformly stirring;
3) transferring the mixed solution in the step 2) to a reaction kettle for carrying out a solvothermal reaction;
4) centrifugally washing the mixed solution in the step 3), and then drying;
5) grinding the solid obtained in the step 4) to obtain a precursor MIL-88;
6) weighing thioacetamide, adding ethanol to dissolve the thioacetamide to form a uniform solution, adding a precursor MIL-88 into the solution with the concentration of 1-15 g/L, and fully stirring the solution, wherein the stirring time of the mixed solution is 5-60 min;
7) transferring the mixed solution in the step 6) to a reaction kettle for secondary solvothermal reaction;
8) centrifugally washing the mixed solution in the step 7), and then drying;
9) drying and grinding the material obtained in the step 8) to obtain the iron-nickel metal sulfide catalyst derived from the metal organic framework;
in step 1), the iron salt is selected from at least one of ferric chloride hexahydrate, ferric sulfate, ferric nitrate and the like, preferably ferric chloride hexahydrate, and the nickel salt is selected from at least one of nickel nitrate hexahydrate, nickel chloride, nickel acetylacetonate and the like, preferably nickel nitrate hexahydrate; the mass concentration of the ferric salt is 1-50 g/L, the mass concentration of the nickel salt is 1-50 g/L, and the mass concentration of the terephthalic acid is 1-50 g/L; preferably, the mass concentration of the terephthalic acid is 5-25 g/L; the stirring time is 5-60 min, preferably 10-30 min.
In the step 2), the mass concentration of the sodium hydroxide solution is 1-50 g/L, preferably 5-25 g/L; the stirring time is 0.5-8 h, and the stirring time is 1-3 h.
In the step 3), the temperature of the primary solvothermal reaction is 60-150 ℃, and the reaction time is 1-24 h; the preferable reaction temperature is 80-120 ℃, and the reaction time is 12-18 h.
In the step 4), the drying temperature is 30-95 ℃, and the drying time is 0.5-1.5 d; preferably, the drying temperature is 50-70 ℃, and the drying time is 0.7-1.2 d.
In the step 6), the mass concentration of thioacetamide is 1-15 g/L, and the stirring time is 5-60 min; preferably, the mass concentration of the thioacetamide is 5-10 g/L, and the stirring time is 10-30 min.
In the step 7), the reaction temperature is 60-180 ℃, and the reaction time is 1-48 h; the preferable reaction temperature is 90-160 ℃, and the reaction time is 3-24 h.
In the step 8), the drying temperature is 30-95 ℃, and the drying time is 0.5-1.5 d; preferably, the drying temperature is 50-70 ℃, and the drying time is 0.7-1.2 d.
The iron-nickel metal sulfide catalyst pore channel structure contains more mesopores, is beneficial to the adsorption of water molecules and the precipitation of oxygen in the reaction process, and can be applied to the oxygen precipitation reaction of electrolyzed water.
The specific method of the application can be as follows: the prepared iron-nickel metal sulfide catalyst is used in an electrocatalytic oxygen evolution reaction, the temperature is 10-50 ℃, and the scanning speed is 1-20 mV/s in the presence of the prepared iron-nickel metal sulfide catalyst, so that high activity and high stability are realized.
Compared with the prior art, the invention has the beneficial effects that:
1. the main active substance of the catalyst prepared by the invention is iron-nickel metal sulfide, and the appearance of the catalyst is of a uniform rod-shaped structure. Under the reaction condition, the iron-nickel metal sulfide generates hydroxyl oxidation species in situ, so that the increase of active species is promoted, and the two species generate synergistic action, so that the oxygen evolution reaction activity is promoted.
2. The pore structure of the catalyst prepared by the invention contains more mesopores, which is beneficial to the adsorption of water molecules and the separation of oxygen in the reaction process and promotes the oxygen evolution reaction.
3. The catalyst prepared by the method is a non-noble metal catalyst, has low cost, abundant raw materials and simple preparation process, and has electrochemical performance superior to most of reported oxygen evolution reaction catalysts and noble metal Ir-based catalysts.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the iron-nickel metal sulfide catalyst prepared in example 1;
FIG. 2 is a Transmission Electron Micrograph (TEM) of the iron-nickel metal sulfide catalyst prepared in example 1 (left panel) and the electrochemically activated iron-nickel metal sulfide catalyst (right panel);
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) of the iron-nickel metal sulfide catalyst prepared in example 1 and the electrochemically activated iron-nickel metal sulfide catalyst;
FIG. 4 is a plot of the linear voltammetry scans for the iron nickel metal sulfide catalysts prepared in examples 2-4 at different sulfidation temperatures;
FIG. 5 is a plot of the linear voltammetry scans for the Fe-Ni metal sulfide catalysts prepared in examples 1, 3, 5-7 at different sulfidation durations;
FIG. 6 is a chronopotentiometric chart of the iron-nickel metal sulfide catalyst prepared in example 1.
Detailed Description
The following embodiments will further illustrate and describe the technical solutions of the present invention with reference to the accompanying drawings. The following examples are given by way of illustration only and the present disclosure is not limited thereto.
In the following examples, the voltage scaling and overpotential in the oxygen evolution reaction test are defined by the following equations:
ERHE＝ESCE+0.244+0.059×pH
before each test, the catalyst was activated by scanning 10 cycles of cyclic voltammetry in the test interval at a current density of 10mA/cm2The corresponding overpotential is used as the standard for evaluating the oxygen evolution reaction activity
The instrument used to analyze the electrocatalytic performance of the catalyst was the CHI660E electrochemical workstation.
Example 1
(1) Weighing 0.811g of ferric chloride hexahydrate, 0.872g of nickel nitrate hexahydrate and 0.997g of terephthalic acid, dissolving in 60mL of N, N-dimethylformamide, and stirring for 30min to form a uniform solution;
(2) measuring 12mL of sodium hydroxide solution, adding the sodium hydroxide solution into the solution obtained in the step (1), and stirring for 3 hours until the solution is uniform, wherein the concentration of the sodium hydroxide solution is 16 g/L;
(3) transferring the mixed solution in the step (2) into a reaction kettle for solvothermal reaction at 100 ℃ for 15 hours;
(4) centrifugally washing (water washing and alcohol washing) the mixed solution in the step (3), and then drying in an oven at 70 ℃ overnight;
(5) grinding the solid obtained in the step (4) to obtain a precursor MIL-88;
(6) weighing 0.450g of thioacetamide, adding 60mL of ethanol for dissolving to form a uniform solution, adding 0.1g of precursor MIL-88, and fully stirring for 30 min;
(7) transferring the mixed solution in the step (6) into a reaction kettle for solvothermal reaction at 120 ℃ for 12 hours;
(8) carrying out centrifugal washing (alcohol washing) on the mixed solution in the step (7), and then carrying out overnight drying in an oven at 70 ℃;
(9) drying and grinding the material obtained in the step (8) to obtain the iron-nickel metal sulfide catalyst derived from the metal organic framework
(10) Preparation of catalyst ink and preparation of working electrode: adding 3mg of catalyst and 1mg of commercial carbon black into 990 mu L of ethanol water solution (ethanol: water: 1), performing ultrasonic treatment for 1h, adding 10 mu L of 5 wt% Nafion solution, and performing ultrasonic treatment for 30min to obtain catalyst ink; uniformly coating 10 mu L of catalyst ink on the surface (with the diameter of 5mm) of the polished glassy carbon electrode, and naturally drying at room temperature to obtain a working electrode;
(11) adopting a three-electrode system to carry out electrocatalysis reaction, taking a glassy carbon electrode coated with ink as a working electrode, a saturated calomel electrode as a reference electrode, and a carbon rod as a counter electrode; measuring 60mL of potassium hydroxide solution (with the concentration of 1.0M) as electrolyte;
(12) taking a CHI660E electrochemical workstation as a power supply, adopting a linear sweep voltammetry for activity evaluation, and taking a sweep rate of 10 mV/s; the stability test adopts a constant current method, and the performance of the catalyst is 10mA/cm2The corresponding potential is a voltage condition.
FIG. 1 is an X-ray diffraction pattern (XRD) of the iron-nickel metal sulfide catalyst prepared in example 1. As seen from FIG. 1, the catalyst has five characteristic peaks at 30.2 °, 32.8 °, 36.8 °, 48.0 °, and 52.6 °, corresponding to pyrite (Fe, Ni) S2The (200), (210), (211), (220) and (311) crystal faces (JCPDF #02-0850) of the phases have the peak position shift because the main metal element of the precursor MOF is an iron element, the content of nickel in the catalyst is low, and the sulfide derived from the metal organic framework can effectively improve the conductivity of the material and improve the activity of oxygen evolution reaction.
Fig. 2 is a Transmission Electron Micrograph (TEM) of the iron-nickel metal sulfide catalyst prepared in example 1 and the electrochemically activated iron-nickel metal sulfide catalyst. As shown in figure 2, the catalyst has a uniform rod-like shape, the length of the catalyst is about 840nm, the width of the catalyst is about 210nm, and after cyclic voltammetry scanning activation, an amorphous structure is newly generated on the surface, so that active sites are increased, and the improvement of oxygen evolution reaction activity is promoted.
Fig. 3 is an X-ray photoelectron spectroscopy (XPS) of the iron-nickel metal sulfide catalyst prepared in example 1 and the iron-nickel metal sulfide catalyst subjected to electrochemical activation. As shown in FIG. 3, after cyclic voltammetry scanning activation, peaks at 857.8eV and 876.2eV appear in the spectrum of Ni 2p of the catalyst, which correspond to Ni3+2p of3/2Track and 2p1/2Orbitals, indicating the formation of nickel oxyhydroxide species, in situ generated hydroxyl groupsThe oxidizing species can promote the adsorption and conversion of the reaction intermediates by the catalyst.
FIG. 6 chronopotentiometric chart of iron-nickel metal sulfide catalyst prepared in example 1. From FIG. 6 it can be seen that the catalyst concentration can be at 10mA/cm2The reaction is stable for 40 hours under the condition of (1), and the reaction time is far more than 12 hours of that of a noble metal catalyst Ir/C, which shows that the catalyst has excellent stability.
Example 2
Similar to example 1, the difference is that the temperature of the second solvothermal reaction in step (7) is changed to 100 ℃ and the reaction time is changed to 6h, and the other steps are carried out by the method of example 1, thus obtaining the catalyst of the invention.
Example 3
Similar to example 1, the difference is that the second solvothermal reaction time in step (7) is changed to 6h, and the other steps are carried out by the method of example 1, to obtain the catalyst of the present invention.
Example 4
Similar to example 1, the difference is that the temperature of the second solvothermal reaction in step (7) is changed to 120 ℃ to 150 ℃ and the reaction time is changed to 6h, and the other steps are carried out by the method of example 1, thus obtaining the catalyst of the invention.
FIG. 4 is a plot of the linear voltammetry scans for the iron nickel metal sulfide catalysts prepared in examples 2-4 at different sulfidation temperatures. As can be seen from fig. 4, the oxygen evolution reactivity of the catalyst increased first and then decreased with increasing sulfidation temperature, with the optimum sulfidation temperature being 120 ℃.
Example 5
Similar to example 1, the difference is that the reaction time in step (7) is changed from 12h to 3h, and the other steps are carried out by the method of example 1, to obtain the catalyst of the present invention.
Example 6
Similar to example 1, the difference is that the reaction time in step (7) is changed from 12h to 18h, and the other steps are carried out by the method of example 1, to obtain the catalyst of the present invention.
Example 7
Similar to example 1, except that the reaction time in step (7) was changed from 12 hours to 24 hours, the other steps were carried out by the method of example 1, to obtain the catalyst of the present invention.
FIG. 5 is a plot of the linear voltammetry scans for the Fe-Ni metal sulfide catalysts prepared in examples 1, 3, 5-7 at different sulfidation durations. As can be seen from FIG. 5, the oxygen evolution reaction performance of the catalyst exhibited an increasing and decreasing performance with increasing sulfidation time, with the optimum sulfidation time being 12 hours and the optimum catalyst being at 10mA/cm2The overpotential is only 247mV at the current density of (1).
Example 8
Similar to example 1, except that the iron salt in step (1) was selected to be ferric nitrate nonahydrate and the nickel salt was selected to be nickel chloride hexahydrate, and the other steps were carried out by the method of example 1, to obtain the catalyst of the present invention.
Example 9
Similar to example 1, except that in step (1), the mass of iron salt is 1.081g, the mass of nickel salt is 0.582g, and other steps are carried out by the method of example 1, and the catalyst of the present invention is obtained.
Example 10
Similar to example 1, except that 0.541g of iron salt and 1.163g of nickel salt were weighed in step (1), the other steps were carried out by the method of example 1, and the catalyst of the present invention was obtained.
Example 11
Similar to example 1, except that the mass of terephthalic acid in step (1) was 1.496g, the other steps were carried out in the same manner as in example 1, to obtain the catalyst of the present invention.
Example 12
Similar to example 1, except that the concentration of the sodium hydroxide solution in step (2) was 24g/L, the other steps were carried out by the method of example 1, to obtain a catalyst of the present invention.
Example 13
Similar to example 1, the difference is that the temperature of the first solvothermal reaction in step (3) was changed from 100 ℃ to 80 ℃, and the other steps were carried out by the method of example 1, to obtain the catalyst of the present invention.
Example 14
Similar to example 1, the difference is that the temperature of the first solvothermal reaction in step (3) is changed from 100 ℃ to 120 ℃, and the other steps are carried out by the method of example 1, to obtain the catalyst of the present invention.
Example 15
Similar to example 1, the difference is that the reaction time in step (3) is changed from 15h to 12h, and the other steps are carried out by the method of example 1, to obtain the catalyst of the present invention.
Example 16
Similar to example 1, the difference is that the reaction time in step (3) is changed from 15h to 18h, and the other steps are carried out by the method of example 1, to obtain the catalyst of the present invention.
Example 17
Similar to example 1, except that 0.3g of thioacetamide was weighed out in step (6), the other steps were carried out in the same manner as in example 1 to obtain the catalyst of the present invention.
Example 18
Similar to example 1, except that 0.6g of thioacetamide was weighed in the step (6), the other steps were performed by the method of example 1 to obtain the catalyst of the present invention.
Example 19
Similar to example 1, the difference is that the drying temperature in step (4) and step (9) is 60 ℃, the drying time is 1d, and the other steps are carried out by the method of example 1, and the catalyst of the present invention is obtained.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318358A (en) * | 2021-11-10 | 2022-04-12 | 青岛科技大学 | Modulated nickel/cobalt bimetallic MOF-based electrocatalyst, preparation method and application |
| CN115286806A (en) * | 2022-01-24 | 2022-11-04 | 昆明理工大学 | Application method and preparation method of metal organic framework (OER) nanomaterial regulated by phenolic hydroxyl group |
| CN115522215A (en) * | 2022-10-09 | 2022-12-27 | 蔡磊 | Preparation and Application of MIL-88@CoMg Hydrogen Evolution Catalyst for Electrolysis of Water Based on Nickel Foam |
| CN115874213A (en) * | 2022-11-11 | 2023-03-31 | 石河子大学 | Preparation method of fast in-situ synthesis hydroxyl oxide electrocatalyst |
| CN118616060A (en) * | 2024-05-31 | 2024-09-10 | 南京理工大学 | A carbon-coated iron-nickel metal sulfide and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321366A (en) * | 2017-06-15 | 2017-11-07 | 北京科技大学 | A kind of elctro-catalyst of efficient-decomposition aquatic products hydrogen production oxygen and preparation method thereof |
| CN110270351A (en) * | 2018-03-13 | 2019-09-24 | 吉林师范大学 | A kind of alkaline water electrolytic of high nickel content pentlandite phase nickel cobalt sulphide electrocatalyst and preparation method thereof |
| CN112023946A (en) * | 2020-09-08 | 2020-12-04 | 河南师范大学 | A kind of preparation method of self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst |
-
2021
- 2021-02-01 CN CN202110136312.5A patent/CN112899723B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107321366A (en) * | 2017-06-15 | 2017-11-07 | 北京科技大学 | A kind of elctro-catalyst of efficient-decomposition aquatic products hydrogen production oxygen and preparation method thereof |
| CN110270351A (en) * | 2018-03-13 | 2019-09-24 | 吉林师范大学 | A kind of alkaline water electrolytic of high nickel content pentlandite phase nickel cobalt sulphide electrocatalyst and preparation method thereof |
| CN112023946A (en) * | 2020-09-08 | 2020-12-04 | 河南师范大学 | A kind of preparation method of self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst |
Non-Patent Citations (2)
| Title |
|---|
| PENGSONG LI: "A multiphase nickel iron sulfide hybrid electrode for highly active oxygen evolution", 《SCI CHINA MATER》 * |
| YUNMEI DU: "Nickel-iron phosphides nanorods derived from bimetallic-organic frameworks for hydrogen evolution reaction", 《APPLIED SURFACE SCIENCE》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318358A (en) * | 2021-11-10 | 2022-04-12 | 青岛科技大学 | Modulated nickel/cobalt bimetallic MOF-based electrocatalyst, preparation method and application |
| CN115286806A (en) * | 2022-01-24 | 2022-11-04 | 昆明理工大学 | Application method and preparation method of metal organic framework (OER) nanomaterial regulated by phenolic hydroxyl group |
| CN115286806B (en) * | 2022-01-24 | 2023-09-19 | 昆明理工大学 | Application method and preparation method of phenolic hydroxyl-regulated metal organic framework nanomaterial OER |
| CN115522215A (en) * | 2022-10-09 | 2022-12-27 | 蔡磊 | Preparation and Application of MIL-88@CoMg Hydrogen Evolution Catalyst for Electrolysis of Water Based on Nickel Foam |
| CN115522215B (en) * | 2022-10-09 | 2024-11-12 | 典石科技(常州)有限公司 | Preparation method of MIL-88@CoMg water electrolysis hydrogen evolution catalyst based on nickel foam |
| CN115874213A (en) * | 2022-11-11 | 2023-03-31 | 石河子大学 | Preparation method of fast in-situ synthesis hydroxyl oxide electrocatalyst |
| CN118616060A (en) * | 2024-05-31 | 2024-09-10 | 南京理工大学 | A carbon-coated iron-nickel metal sulfide and its preparation method and application |
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