CN115557473B - Preparation method of double-component nano heterojunction material with coherent growth characteristics - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 230000001427 coherent effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 28
- 229910052723 transition metal Inorganic materials 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 150000003624 transition metals Chemical group 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- -1 transition metal sulfide Chemical class 0.000 claims description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- LDSUEKXPKCHROT-UHFFFAOYSA-N cyclopenta-1,3-diene-1-carboxylic acid;iron(2+) Chemical compound [Fe+2].OC(=O)C1=CC=C[CH-]1.OC(=O)C1=CC=C[CH-]1 LDSUEKXPKCHROT-UHFFFAOYSA-N 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 239000007769 metal material Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 241000252073 Anguilliformes Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/0622—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with iron, cobalt or nickel
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
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Abstract
The invention discloses a preparation method of a double-component nano heterojunction material with coherent growth characteristics, which comprises the steps of firstly synthesizing a ferrocenyl metal-organic framework material through a simple solvothermal reaction, and then obtaining the double-component nano heterojunction material with coherent growth characteristics through chemical conversion; the synthesis method is simple, realizes the construction and structural optimization of various complex heterojunctions, and improves the electrocatalytic oxygen production activity.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a preparation method of a double-component nano heterojunction material with coherent growth characteristics.
Background
The solid-solid interface connects the unrelated materials to a common boundary and bridges the structure, composition and electronic gap between the constituent materials. By means of the synergistic or bifunctional effect between the constituent materials, the adjustment of the adhesion structure and chemical properties of the interface is critical for promoting applications such as catalysis, energy storage, etc. The former mechanism allows for compositional, geometric, electronic and phonon structural modulation of the active phase component by interaction with the carrier component, possibly through the interface in the form of mass transport, charge transfer, strain effects and thermal conduction, respectively. The latter mechanism allows integration of the unique functions of the individual components, which share a common interface for catalyzing successive chemical reactions, effecting tandem catalysis.
A more interesting fact is that one interface naturally leads to abrupt termination of one lattice and extension of the other lattice, thus introducing a local structure different from both lattices. The interconnection of different networks of crystal structures at the interface imparts such a local structure with a significantly altered coordination environment and electronic structure compared to its corresponding parent structure, which results in the creation of new catalytically active sites that exceed the geometric and compositional limitations of either constituent species. Therefore, by continuously grafting two crystalline phases together and forming a double-component nano heterojunction with coherent growth characteristics, a metastable local interface structure can be created, and the double-component nano heterojunction has great application prospect in the aspects of catalysis, energy storage and the like as an active site capable of effectively absorbing, activating and converting reactant molecules and releasing product molecules. However, from a chemical synthesis point of view, homogeneous grafting with coherent interfacial nano-heterostructures faces serious challenges, since most of the nano-heterojunction materials reported are obtained by simple post-synthesis modification methods, which limits to a large extent their nano-scale composition and structural uniformity.
In view of this, we propose an effective strategy in the present invention to bond metallocene-based ligands to metal cations via coordination bonds to form metal-organic framework materials (Fc-MOFs) with periodic topologies. Fc-MOFs can be used to synthesize in situ, by specific chemical transformations (oxidation, phosphating, sulfidation, nitridation, selenization, etc.), a two-component nano-heterojunction material with coherent growth characteristics. In the strategy, the effective regulation and control of the components in the two-component nano heterojunction material can be successfully realized by adjusting the components of metal cations and chemical conversion conditions, and excellent electrochemical performance is shown.
Disclosure of Invention
The invention provides a preparation method of a double-component nano heterojunction material with coherent growth characteristics, which successfully synthesizes a coherent growth transition metal-based nano heterojunction material, such as: co-grown bi-component transition metal oxide heterojunction, transition metal phosphide heterojunction, transition metal sulfide, transition metal nitride and transition metal selenide heterojunction. The co-grown bi-component nano heterojunction material has the advantages of simple synthesis, adjustable structural components, higher OER electrocatalytic activity and good electrocatalytic stability.
The technical scheme of the invention is as follows:
a preparation method of a double-component nano heterojunction material with coherent growth characteristics comprises the following steps:
placing an Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, introducing a non-metal source material, setting the temperature of the high-temperature tube furnace to 300-800 ℃, and carrying out constant-temperature reaction for 1-4 hours to obtain the two-component nano heterojunction material;
the nonmetallic source material is air, phosphorus source material, sulfur source material, selenium powder or ammonia gas;
the Fc-MOF precursor is prepared by the following method:
dissolving metal salt in deionized water to obtain a metal salt solution; dissolving a ligand containing a metal pi bond in N, N-Dimethylformamide (DMF) to obtain a ligand solution; mixing the obtained metal salt solution with a ligand solution, performing hydrothermal reaction for 4-24 hours at 100-180 ℃, centrifuging, washing (respectively washing with DMF and deionized water), and drying (60 ℃) to obtain an Fc-MOF precursor;
the ratio of the metal salt, ligand and solvent (total of deionized water and N, N-dimethylformamide) was 1 (mmol): 1 (mmol): 5-20 (mL); in the solvent, the volume ratio of N, N-dimethylformamide to deionized water is 2:1, a step of;
the metal salt is selected from transition metals of Fe, co, ni, cu, zn, mn, la, ce, pr, nd, sm, eu, gd, tb, dy, er, tm, yb, zr-based metal nitrate, chloride or sulfate; preferably, the metal salt is formed by mixing Fe-based metal salt and Co, ni, cu, zn, mn, la, ce, pr, nd, sm, eu, gd, tb, dy, er, tm, yb and Zr-based metal salt according to any proportion;
the ligand is 1,1' -ferrocenedicarboxylic acid.
Further, when the nonmetallic source material is air, the preparation method of the two-component nano heterojunction material with the coherent growth characteristic comprises the following steps: and placing the Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, setting the temperature of the high-temperature tube furnace to be 500-800 ℃ in air atmosphere, and carrying out constant-temperature reaction for 1-4 h to obtain the transition metal oxide nano heterojunction.
Further, when the nonmetallic source material is a phosphorus source material, the preparation method of the two-component nano heterojunction material with the coherent growth characteristic comprises the following steps: placing an Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, placing a phosphorus source material on the upstream of the gas, setting the temperature of the high-temperature tube furnace to 300-600 ℃ under inert atmosphere, and carrying out constant-temperature reaction for 1-4 h to obtain a transition metal phosphide nano heterojunction;
the phosphorus source material is, for example: phosphorus powder, sodium hypophosphite and potassium hypophosphite;
the mass ratio of the Fc-MOF precursor to the phosphorus source material is 1:10 to 50 percent.
Further, when the nonmetallic source material is a sulfur source material, the preparation method of the two-component nano heterojunction material with the coherent growth characteristic comprises the following steps: placing an Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, placing a sulfur source material on the upstream of the gas, setting the temperature of the high-temperature tube furnace to 300-700 ℃ under inert atmosphere, and carrying out constant-temperature reaction for 1-4 h to obtain a transition metal sulfide nano heterojunction;
the sulfur source material is, for example: sulfur powder, thiourea;
the mass ratio of the Fc-MOF precursor to the sulfur source material is 1:10 to 50 percent.
Further, when the nonmetallic source material is selenium powder, the preparation method of the two-component nano heterojunction material with the coherent growth characteristic comprises the following steps: placing the Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, placing selenium powder on the upstream of the gas, setting the temperature of the high-temperature tube furnace to 300-500 ℃ under inert atmosphere, and carrying out constant-temperature reaction for 1-4 h to obtain a transition metal selenide nano heterojunction;
the mass ratio of the Fc-MOF precursor to the selenium powder is 1:4 to 20.
Further, when the nonmetallic source material is ammonia gas, the preparation method of the two-component nano heterojunction material with the coherent growth characteristic comprises the following steps: and (3) placing the Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, taking ammonia gas as reaction gas, setting the temperature of the high-temperature tube furnace to 300-500 ℃ under the protection of inert atmosphere, and carrying out constant-temperature reaction for 1-4 hours to obtain the transition metal nitride nano heterojunction.
The double-component nano heterojunction material with coherent growth characteristics can be used as an electrocatalyst for oxygen precipitation reaction under alkaline conditions.
The invention has the advantages and effects that:
1. the ferrocenyl metal organic framework material is synthesized through simple solvothermal reaction, and then the double-component nano heterojunction material with the coherent growth characteristic is obtained through chemical conversion. The synthesis method is simple, meanwhile, the construction and the structural optimization of complex heterojunctions with various types are realized, and the operation is convenient.
2. The double-component nano heterojunction material with coherent growth characteristics is prepared by the invention, the component types and the proportion are adjustable, and the double-component nano heterojunction material has rich interfaces under the nanoscale. Optimizing the catalytic activity of metal sites at the interface and improving the activity of electrocatalytic oxygen production sites.
3. In the form of synthesized NiSe 2 /FeSe 2 The plate-like junction nano heterojunction catalyst is exemplified and shows excellent electrocatalytic oxygen precipitation reaction activity.
4. By synthesized NiO/Fe 3 O 4 The plate-like junction nano heterojunction catalyst is exemplified and shows excellent electrocatalytic oxygen precipitation reaction activity.
5. The material prepared by the invention belongs to non-noble metal-based materials, and has low cost.
Drawings
FIG. 1 is an Fc-MOF derived NiSe 2 /FeSe 2 EDS Mapping and EELS Mapping diagrams of nano heterojunction.
FIG. 2 is NiSe 2 /FeSe 2 XRD pattern of the nano-heterojunction.
FIG. 3 is NiSe 2 /FeSe 2 High resolution electron microscope characterization of nano heterojunction (scale 1 nm).
FIG. 4 is a catalyst NiSe 2 /FeSe 2 Nanometer heterojunction and commercial RuO 2 Linear Sweep Voltammetry (LSV) curve contrast plot for the modified electrode.
FIG. 5 is a catalyst NiSe 2 /FeSe 2 The nanometer heterojunction modifies the timing potential diagram of the electrode under different current densities.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific embodiments so that those skilled in the art may better understand the implementation of the present invention, but the scope of the present invention is not limited thereto.
The raw materials used in the embodiment of the invention are all commercial materials unless specified otherwise; unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1NiSe 2 /FeSe 2 Is prepared from
1. 1mmol of nickel chloride was first dissolved in 4mL of deionized water, and then 1mmol of 1,1' -ferrocenyldimethyl acid was dissolved in 8mL of N, N-dimethylformamide. Mixing the solutions, transferring the mixed solutions into a polytetrafluoroethylene reaction kettle, reacting for 12 hours at 120 ℃, centrifuging, washing the mixed solutions with DMF and deionized water respectively, and placing the products in an oven for drying at 60 ℃ to obtain ferrocenyl MOF (NiFe-MOF);
2. 10mg of NiFe-MOF precursor was placed in the center of the warm zone of the high temperature tube furnace and 40mg of selenium powder was placed upstream of the gas. Setting the temperature of a high-temperature tube furnace to 350 ℃ in Ar atmosphere, and carrying out constant-temperature reaction for 2 hours to finally obtain NiSe 2 /FeSe 2 A nano heterojunction.
3. 2.5mg of the catalyst prepared in the example, 2.5mg of commercial carbon black was respectively dispersed in isopropyl alcohol-Nafion mixed solution (0.9 mL of isopropyl alcohol and 0.1mL of 0.5% Nafion solution were mixed), and after 2 hours of ultrasonic treatment, a catalyst solution was obtained which was uniformly dispersed;
4. dripping 10ul of catalyst solution on the glassy carbon electrode, and naturally air-drying to obtain a catalyst modified glassy carbon electrode;
5. electrochemical testing was performed on the CHI760E electrochemical workstation. The catalyst modified glassy carbon electrode is used as a working electrode, the Pt net is used as a counter electrode, and Hg/HgO is used as a reference electrode. At O 2 A Linear Sweep Voltammetric (LSV) test of the oxygen evolution reaction was performed with saturated 1M KOH solution.
As shown in FIG. 1, niSe 2 And FeSe 2 Nano heterojunction in NiSe 2 /FeSe 2 And is highly dispersed uniformly.
As shown in FIG. 2, niSe 2 /FeSe 2 The nano heterojunction is formed by NiSe 2 And FeSe 2 Two phases.
As shown in FIG. 3, niSe 2 And FeSe 2 The nano heterojunction has coherent growth characteristics.
As shown in FIG. 4, niSe 2 /FeSe 2 Nano heterojunction electrodes have advantages over commercial RuO 2 And OER catalytic activity of transition metal based materials reported in most literature. At 10mA cm -2 NiSe at a current density of (C) 2 /FeSe 2 The nano-heterojunction electrode only required an overpotential of 246.1mV, whereas commercial RuO 2 The electrode requires an overpotential of 320 mV.
As shown in FIG. 5, niSe 2 /FeSe 2 The nano heterojunction electrode has excellent stability, and can be used for preparing a nano heterojunction electrode with the concentration of 10mA cm -2 ，50mA cm -2 And 100mA cm -2 After 48h of test at current density of (c), the overpotential hardly increased.
EXAMPLE 2NiO/Fe 3 O 4 Is prepared from
1. Step 1 as in embodiment 1;
2. 10mg of NiFe-MOF precursor is placed in the center of a temperature zone of a high-temperature tube furnace, the temperature of the high-temperature tube furnace is set to 700 ℃ in air atmosphere, and the reaction is carried out for 2 hours at constant temperature, so that NiO/Fe is finally obtained 3 O 4 A nano heterojunction.
3.NiO/Fe 3 O 4 The nanometer heterojunction electrode has advantagesIn commercial RuO 2 And OER catalytic activity of transition metal based materials reported in most literature. At 10mA cm -2 NiO/Fe at current density of (3) 3 O 4 The nano heterojunction electrode only requires an overpotential of 260.8mV, whereas commercial RuO 2 The electrode requires an overpotential of 320 mV.
EXAMPLE 3Ni 2 P/Fe 2 Preparation of P
1. Step 1 as in embodiment 1;
2. 10mg of NiFe-MOF precursor was placed in the center of the warm zone of the high temperature tube furnace and 500mg of sodium hypophosphite was placed upstream of the gas. Setting the temperature of a high-temperature tube furnace to 400 ℃ in Ar atmosphere, and carrying out constant-temperature reaction for 4 hours to finally obtain Ni 2 P/Fe 2 P nano heterojunction.
3.Ni 2 P/Fe 2 P nano heterojunction electrode has advantages over commercial RuO 2 And OER catalytic activity of transition metal based materials reported in most literature. At 10mA cm -2 At a current density of Ni 2 P/Fe 2 The P-nano heterojunction electrode only required 249.4mV overpotential, whereas commercial RuO 2 The electrode requires an overpotential of 320 mV.
EXAMPLE 4Ni 2 S/Fe 2 Preparation of S
1. Step 1 as in embodiment 1;
2. 10mg of NiFe-MOF precursor was placed in the center of the warm zone of a high temperature tube furnace and 200mg of sulfur powder was placed upstream of the gas. Setting the temperature of a high-temperature tube furnace to be 500 ℃ in Ar atmosphere, and carrying out constant-temperature reaction for 4 hours to finally obtain Ni 2 S/Fe 2 S nanometer heterojunction.
3.Ni 2 S/Fe 2 S nano heterojunction electrode has advantages over commercial RuO 2 And OER catalytic activity of transition metal based materials reported in most literature. At 10mA cm -2 At a current density of Ni 2 S/Fe 2 The S nano heterojunction electrode only requires an overpotential of 257.4mV, whereas commercial RuO 2 The electrode requires an overpotential of 320 mV.
EXAMPLE 5Ni 3 N/Fe 3 Preparation of N
1. Step 1 as in embodiment 1;
2. 10mg of NiFe-MOF precursor is placed in the center of a warm zone of a high-temperature tube furnace, NH 3 The reaction gas, ar gas is used as protective gas, the temperature of the high-temperature tube furnace is set to 400 ℃, the reaction is carried out for 4 hours at constant temperature, and finally Ni is obtained 3 N/Fe 3 N nanometer heterojunction.
3.Ni 3 N/Fe 3 N-nanometer heterojunction electrodes have advantages over commercial RuO 2 And OER catalytic activity of transition metal based materials reported in most literature. At 10mA cm -2 NiSe at a current density of (C) 2 /FeSe 2 The nano-heterojunction electrode only required an overpotential of 252.6mV, whereas commercial RuO 2 The electrode requires an overpotential of 320 mV.
Comparative example
As shown in the following table, compared with the OER catalytic activity of the transition metal-based material widely reported in the literature, the two-component nano heterojunction material with the coherent growth characteristic prepared by the invention has more excellent performance. At 10mA cm -2 NiSe at a current density of (C) 2 /FeSe 2 The nano-heterojunction electrode only requires an overpotential of 246.1mV, which is lower than that required for most transition metal-based materials at the corresponding current densities.
Claims (9)
1. The preparation method of the double-component nano heterojunction material with the coherent growth characteristic is characterized by comprising the following steps of:
placing an Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, introducing a non-metal source material, setting the temperature of the high-temperature tube furnace to 300-800 ℃, and carrying out constant-temperature reaction for 1-4 hours to obtain the two-component nano heterojunction material;
the nonmetallic source material is air, phosphorus source material, sulfur source material, selenium powder or ammonia gas;
the Fc-MOF precursor is prepared by the following method:
dissolving metal salt in deionized water to obtain a metal salt solution; dissolving a ligand containing a metal pi bond in N, N-dimethylformamide to obtain a ligand solution; mixing the obtained metal salt solution with a ligand solution, performing hydrothermal reaction for 4-24 hours at 100-180 ℃, centrifuging, washing and drying to obtain an Fc-MOF precursor;
the metal salt is transition metal Co, ni, cu, zn, mn, zr-based metal nitrate, chloride or sulfate;
the ligand is 1,1' -ferrocenedicarboxylic acid.
2. The method for preparing a two-component nano heterojunction material with coherent growth characteristics as claimed in claim 1, wherein in the method for preparing an Fc-MOF precursor, the ratio of the metal salt, the ligand and the solvent is 1mmol:1mmol: 5-20 mL; in the solvent, the volume ratio of N, N-dimethylformamide to deionized water is 2:1.
3. the method for preparing the two-component nano heterojunction material with the coherent growth characteristic according to claim 1, wherein when the nonmetallic source material is air, the method for preparing the two-component nano heterojunction material with the coherent growth characteristic is as follows: and placing the Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, setting the temperature of the high-temperature tube furnace to be 500-800 ℃ in air atmosphere, and carrying out constant-temperature reaction for 1-4 h to obtain the transition metal oxide nano heterojunction.
4. The method for preparing the two-component nano heterojunction material with the coherent growth characteristic according to claim 1, wherein when the nonmetallic source material is a phosphorus source material, the method for preparing the two-component nano heterojunction material with the coherent growth characteristic is as follows: placing an Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, placing a phosphorus source material on the upstream of the gas, setting the temperature of the high-temperature tube furnace to 300-600 ℃ under inert atmosphere, and carrying out constant-temperature reaction for 1-4 h to obtain a transition metal phosphide nano heterojunction;
the phosphorus source material is selected from: phosphorus powder, sodium hypophosphite and potassium hypophosphite;
the mass ratio of the Fc-MOF precursor to the phosphorus source material is 1:10 to 50 percent.
5. The method for preparing the two-component nano heterojunction material with the coherent growth characteristic according to claim 1, wherein when the nonmetallic source material is a sulfur source material, the method for preparing the two-component nano heterojunction material with the coherent growth characteristic is as follows: placing an Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, placing a sulfur source material on the upstream of the gas, setting the temperature of the high-temperature tube furnace to 300-700 ℃ under inert atmosphere, and carrying out constant-temperature reaction for 1-4 h to obtain a transition metal sulfide nano heterojunction;
the sulfur source material is selected from: sulfur powder, thiourea;
the mass ratio of the Fc-MOF precursor to the sulfur source material is 1:10 to 50 percent.
6. The method for preparing the two-component nano heterojunction material with the coherent growth characteristic according to claim 1, wherein when the nonmetallic source material is selenium powder, the method for preparing the two-component nano heterojunction material with the coherent growth characteristic is as follows: placing the Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, placing selenium powder on the upstream of the gas, setting the temperature of the high-temperature tube furnace to 300-500 ℃ under inert atmosphere, and carrying out constant-temperature reaction for 1-4 h to obtain a transition metal selenide nano heterojunction;
the mass ratio of the Fc-MOF precursor to the selenium powder is 1:4 to 20.
7. The method for preparing the two-component nano heterojunction material with the coherent growth characteristic according to claim 1, wherein when the nonmetallic source material is ammonia gas, the method for preparing the two-component nano heterojunction material with the coherent growth characteristic is as follows: and (3) placing the Fc-MOF precursor in the central position of a temperature zone of a high-temperature tube furnace, taking ammonia gas as reaction gas, setting the temperature of the high-temperature tube furnace to 300-500 ℃ under the protection of inert atmosphere, and carrying out constant-temperature reaction for 1-4 hours to obtain the transition metal nitride nano heterojunction.
8. The two-component nano heterojunction material with coherent growth characteristics prepared by the preparation method of any one of claims 1 to 7.
9. The use of the two-component nano heterojunction material with coherent growth characteristics as defined in claim 8 as an electrocatalyst for oxygen evolution reaction under alkaline conditions.
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