CN115557473A - Preparation method of two-component nano heterojunction material with coherent growth characteristic - Google Patents
Preparation method of two-component nano heterojunction material with coherent growth characteristic Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 claims description 18
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- 150000003624 transition metals Chemical group 0.000 claims description 13
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- 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 3
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- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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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Abstract
The invention discloses a preparation method of a two-component nano heterojunction material with coherent growth characteristics, which comprises the steps of synthesizing a ferrocenyl metal organic framework material through a simple solvothermal reaction, and then obtaining the two-component nano heterojunction material with coherent growth characteristics through chemical conversion; the synthesis method is simple, realizes the construction and structure optimization of various complex heterojunctions, and improves the oxygen production activity of electrocatalysis.
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 unrelated materials on a common boundary and bridges the structural, compositional, and electronic gaps between these constituent materials. By means of synergistic or bifunctional effects between the constituent materials, adjustment of the adhesive structure and chemical properties of the interface is crucial for facilitating catalysis, energy storage, and other applications. The former mechanism allows for compositional, geometric, electronic, and phononic structural modulation of the active phase components through interaction with the carrier component, possibly in the form of mass transport, charge transfer, strain effects, and thermal conduction, respectively, across the interface. The latter mechanism allows the integration of the unique functions of the individual components that share a common interface for catalyzing successive chemical reactions, enabling tandem catalysis.
A more interesting fact is that an interface naturally leads to an abrupt termination of one lattice and an extension of the other lattice, thereby introducing local structures different from the two lattices. The interconnection of networks of different crystal structures at the interface gives such local structures a significantly altered coordination environment and electronic structure compared to their corresponding parent structures, which results in the creation of new catalytically active sites that exceed the geometric and compositional constraints of either constituent species. Therefore, two crystal phases are continuously grafted together to form a bi-component nano heterojunction with coherent growth characteristics, a metastable local interface structure can be created, and the bi-component nano heterojunction can be used as an active site capable of effectively absorbing, activating and converting reactant molecules and releasing product molecules, and has great application prospects in the aspects of catalysis, energy storage and the like. However, from the chemical synthesis perspective, uniform grafting with coherent interface nano-heterostructures faces a serious challenge, because most of the reported nano-heterojunction materials are obtained by simple post-synthesis modification methods, which greatly limits the uniformity of their nano-scale composition and structure.
In view of the above, we propose an effective strategy in the present invention to bond the metallocene ligand and the metal cation by coordination bond to form metal organic framework materials (Fc-MOFs) with periodic topological structure. Through specific chemical conversion (oxidation, phosphorization, vulcanization, nitridation, selenization and the like), fc-MOFs can be used for in-situ synthesis of two-component nano heterojunction materials with coherent growth characteristics. In the strategy, effective regulation and control of components in the two-component nano heterojunction material can be successfully realized by regulating 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: a co-grown two-component transition metal oxide heterojunction, transition metal phosphide heterojunction, transition metal sulfide, transition metal nitride, and transition metal selenide heterojunction. The coherent growth bi-component nano heterojunction material is simple to synthesize, adjustable in structural component, high in OER electrocatalytic activity and good in electrocatalytic stability.
The technical scheme of the invention is as follows:
a preparation method of a two-component nano heterojunction material with coherent growth characteristics comprises the following steps:
placing the Fc-MOF precursor in the center 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 be 300-800 ℃, and reacting at constant temperature for 1-4 h to obtain the two-component nano heterojunction material;
the non-metal source material is air, a phosphorus source material, a sulfur source material, selenium powder or ammonia gas;
the Fc-MOF precursor is prepared by the following method:
dissolving a metal salt in deionized water to obtain a metal salt solution; dissolving a ligand containing metal pi bonds in N, N-Dimethylformamide (DMF) to obtain a ligand solution; mixing the obtained metal salt solution with a ligand solution, carrying out hydrothermal reaction for 4-24 h at 100-180 ℃, then 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 (deionized water and N, N-dimethylformamide in total) is 1 (mmol): 1 (mmol): 5-20 (mL); in the solvent, the volume ratio of the N, N-dimethylformamide to the deionized water is 2:1;
the metal salt is transition metal Fe, co, ni, cu, zn, mn, la, ce, pr, nd, sm, eu, gd, tb, dy, er, tm, yb and Zr-based metal nitrate, chloride salt or sulfate; preferably, the metal salt is formed by mixing Fe-based metal salt with 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' -ferrocene dicarboxylic acid.
Further, when the non-metal source material is air, the preparation method of the two-component nano heterojunction material with coherent growth characteristics comprises the following steps: placing the Fc-MOF precursor in the center of a temperature zone of a high-temperature tubular furnace, setting the temperature of the high-temperature tubular furnace to be 500-800 ℃ in an air atmosphere, and reacting for 1-4 h at constant temperature to obtain the transition metal oxide nano heterojunction.
Further, when the non-metal source material is a phosphorus source material, the preparation method of the two-component nano heterojunction material with coherent growth characteristics comprises the following steps: placing an Fc-MOF precursor at the center of a temperature zone of a high-temperature tubular furnace, placing a phosphorus source material at the upstream of the gas, setting the temperature of the high-temperature tubular furnace to be 300-600 ℃ under an inert atmosphere, and reacting for 1-4 h at constant temperature 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.
Further, when the non-metal source material is a sulfur source material, the preparation method of the two-component nano heterojunction material with coherent growth characteristics comprises the following steps: placing an Fc-MOF precursor in the center of a temperature zone of a high-temperature tube furnace, placing a sulfur source material in the upstream of the gas, setting the temperature of the high-temperature tube furnace to be 300-700 ℃ under inert atmosphere, and reacting for 1-4 h at constant temperature to obtain a transition metal sulfide nano heterojunction;
the sulfur source material is, for example: sulfur powder and thiourea;
the mass ratio of the Fc-MOF precursor to the sulfur source material is 1:10 to 50.
Further, when the non-metal source material is selenium powder, the preparation method of the two-component nano heterojunction material with coherent growth characteristics comprises the following steps: placing an Fc-MOF precursor in the center of a temperature zone of a high-temperature tube furnace, placing selenium powder in the upstream of the gas, setting the temperature of the high-temperature tube furnace to be 300-500 ℃ under inert atmosphere, and reacting for 1-4 h at constant temperature 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 non-metal source material is ammonia gas, the preparation method of the two-component nano heterojunction material with coherent growth characteristics comprises the following steps: placing the Fc-MOF precursor in the center of a temperature zone of a high-temperature tubular furnace, taking ammonia gas as reaction gas, setting the temperature of the high-temperature tubular furnace to be 300-500 ℃ under the protection of inert atmosphere, and reacting for 1-4 h at constant temperature to obtain the transition metal nitride nano heterojunction.
The prepared two-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 invention firstly synthesizes ferrocenyl metal-organic framework material through simple solvothermal reaction, and then obtains the two-component nano heterojunction material with coherent growth characteristic through chemical conversion. The synthesis method is simple, and simultaneously realizes the construction and structure optimization of various complex heterojunctions, thereby being convenient for operation.
2. The prepared double-component nano heterojunction material with coherent growth characteristics has adjustable component types and proportions and abundant interfaces under the nanoscale. The catalytic activity of metal sites at the interface is optimized, and the activity of electrocatalytic oxygen production is improved.
3. To synthesize NiSe 2 /FeSe 2 A sheet-junction nano-heterojunction catalyst, which exhibits excellent electrocatalytic oxygen evolution reactivity, is exemplified.
4. With synthetic NiO/Fe 3 O 4 A sheet-junction nano-heterojunction catalyst, which exhibits excellent electrocatalytic oxygen evolution reactivity, is exemplified.
5. The prepared material belongs to non-noble metal base materials and is low in price.
Drawings
FIG. 1 is Fc-MOF derived NiSe 2 /FeSe 2 EDS Mapping and EELS Mapping of nano-heterojunctions.
FIG. 2 shows NiSe 2 /FeSe 2 XRD pattern of nano-heterojunction.
FIG. 3 is NiSe 2 /FeSe 2 High resolution electron microscopy characterization of nano-heterojunctions (scale 1 nm).
FIG. 4 shows a NiSe catalyst 2 /FeSe 2 Nano-heterojunction and commercial RuO 2 Linear Sweep Voltammetry (LSV) curves versus plots for the modified electrodes.
FIG. 5 shows a catalyst NiSe 2 /FeSe 2 And (3) a chronopotentiometric graph of the electrode under different current densities after the nano heterojunction modification.
Detailed Description
The present invention is further described in the following with reference to the drawings and the specific embodiments so that those skilled in the art can better understand the implementation of the present invention, but the protection scope of the present invention is not limited thereto.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available materials; 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 Preparation of (2)
1. 1mmol of nickel chloride was first dissolved in 4mL of deionized water, and then 1mmol of 1,1' -ferrocene dicarboxylic acid was dissolved in 8mL of N, N-dimethylformamide. Mixing the solutions, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, reacting at 120 ℃ for 12 hours, centrifuging, washing with DMF (dimethyl formamide) and deionized water respectively, and drying the product in an oven at 60 ℃ to obtain ferrocenyl MOF (NiFe-MOF);
2. 10mg of the NiFe-MOF precursor is placed in the center of the temperature zone of the high-temperature tube furnace, and 40mg of selenium powder is placed at the upstream of the gas. In Ar atmosphere, setting the temperature of a high-temperature tube furnace to 350 ℃, 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 and 2.5mg of commercial carbon black are respectively dispersed into isopropanol-Nafion mixed solution (0.9 mL of isopropanol is mixed with 0.1mL of 0.5 percent Nafion solution), and the catalyst solution which is uniformly dispersed is obtained after 2 hours of ultrasonic treatment;
4. dropwise adding 10ul of catalyst solution on the glassy carbon electrode, and naturally drying to obtain a catalyst modified glassy carbon electrode;
5. electrochemical testing was performed on the CHI760E electrochemical workstation. A glassy carbon electrode modified by a catalyst is used as a working electrode, a Pt net is used as a counter electrode, and Hg/HgO is used as a reference electrode. At O 2 Saturated 1M KOH solution was subjected to Linear Sweep Voltammetry (LSV) testing of the oxygen evolution reaction.
As shown in FIG. 1, niSe 2 And FeSe 2 Nano heterojunction in NiSe 2 /FeSe 2 The medium and high degree is uniformly dispersed.
As shown in FIG. 2, niSe 2 /FeSe 2 The nano heterojunction is made of NiSe 2 And FeSe 2 Two phases are formed.
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 The nano heterojunction electrode has better than commercial RuO 2 And OER catalytic activity of most transition metal-based materials reported in the literature. At 10mA cm -2 At a current density of (3), niSe 2 /FeSe 2 The nano-heterojunction electrode only needs an overpotential of 246.1mV, while the 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 at 10mA cm -2 ，50mA cm -2 And 100mA cm -2 After 48h of testing at the current density of (1), the overpotential hardly rises.
Example 2NiO/Fe 3 O 4 Preparation of
1. The same as step 1 of embodiment 1;
2. placing 10mg of NiFe-MOF precursor in the center of a temperature zone of a high-temperature tube furnace, setting the temperature of the high-temperature tube furnace to 700 ℃ in air atmosphere, and carrying out constant-temperature reaction for 2h to finally obtain NiO/Fe 3 O 4 A nano-heterojunction.
3.NiO/Fe 3 O 4 The nano heterojunction electrode has better than commercial RuO 2 And OER catalytic activity of most literature reported transition metal-based materials. At 10mA cm -2 NiO/Fe at a current density of (2) 3 O 4 The nano-heterojunction electrode only requires an overpotential of 260.8mV, whereas the commercial RuO 2 The electrode requires an overpotential of 320 mV.
Example 3Ni 2 P/Fe 2 Preparation of P
1. The same as step 1 of embodiment 1;
2. 10mg of the NiFe-MOF precursor is placed in the center of a temperature zone of a high-temperature tube furnace, and 500mg of sodium hypophosphite is placed at the upstream of the gas. Setting the temperature of the high-temperature tube furnace to 400 ℃ in Ar atmosphere, and carrying out constant-temperature reaction for 4h to finally obtain Ni 2 P/Fe 2 A P nano heterojunction.
3.Ni 2 P/Fe 2 The P nano heterojunction electrode has better performance than commercial RuO 2 And OER catalytic activity of most literature reported transition metal-based materials. At 10mA cm -2 At current density of (2), ni 2 P/Fe 2 The P nano heterojunction electrode only needs 249.4mV over potential, while the commercial RuO 2 The electrode requires an overpotential of 320 mV.
Example 4Ni 2 S/Fe 2 Preparation of S
1. The same as step 1 of embodiment 1;
2. 10mg of the NiFe-MOF precursor was placed in the center of the temperature zone of a high temperature tube furnace, and 200mg of sulfur powder was placed upstream of the gas. In Ar atmosphere, setting the temperature of a high-temperature tube furnace to be 500 ℃, and carrying out constant-temperature reaction for 4h to finally obtain Ni 2 S/Fe 2 And (4) an S nano heterojunction.
3.Ni 2 S/Fe 2 S nano heterojunction electrode with advantages over commercial RuO 2 And OER catalytic activity of most literature reported transition metal-based materials. At 10mA cm -2 At current density of (2), ni 2 S/Fe 2 The S-nano heterojunction electrode only needs 257.4mV of overpotential, while the commercial RuO 2 The electrodes required an overpotential of 320 mV.
Example 5Ni 3 N/Fe 3 Preparation of N
1. The same as step 1 of embodiment 1;
2. placing 10mg of NiFe-MOF precursor in the center of the temperature zone of a high-temperature tube furnace, and placing NH 3 Using Ar gas as protective gas as reaction gas, setting the temperature of the high-temperature tube furnace to 400 ℃, and reacting for 4 hours at constant temperature to finally obtain Ni 3 N/Fe 3 An N-nano heterojunction.
3.Ni 3 N/Fe 3 N nano heterojunction electrode with better than commercial RuO 2 And OER catalytic activity of most literature reported transition metal-based materials. At 10mA cm -2 At a current density of (2), niSe 2 /FeSe 2 The nano-heterojunction electrode only needs 252.6mV of over-potential, while the commercial RuO 2 The electrode requires an overpotential of 320 mV.
Comparative example
As shown in the following table, compared with OER catalytic activity of transition metal-based materials widely reported in the literature, the bi-component nano heterojunction material with coherent growth characteristics prepared by the invention shows more excellent performance. At 10mA cm -2 At a current density of (3), niSe 2 /FeSe 2 The nano-heterojunction electrode only requires an overpotential of 246.1mV, lower than that required for most transition metal-based materials at the corresponding current densities.
Claims (9)
1. A preparation method of a two-component nano heterojunction material with coherent growth characteristics is characterized by comprising the following steps:
placing the Fc-MOF precursor in the center 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 be 300-800 ℃, and reacting at constant temperature for 1-4 h to obtain the two-component nano heterojunction material;
the non-metal source material is air, a phosphorus source material, a sulfur source material, selenium powder or ammonia gas;
the Fc-MOF precursor is prepared by the following method:
dissolving a metal salt in deionized water to obtain a metal salt solution; dissolving a ligand containing metal pi bonds in N, N-dimethylformamide to obtain a ligand solution; mixing the obtained metal salt solution with a ligand solution, carrying out hydrothermal reaction for 4-24 h at 100-180 ℃, then centrifuging, washing and drying to obtain an Fc-MOF precursor;
the metal salt is transition metal Fe, co, ni, cu, zn, mn, la, ce, pr, nd, sm, eu, gd, tb, dy, er, tm, yb and Zr-based metal nitrate, chloride salt or sulfate;
the ligand is 1,1' -ferrocene dicarboxylic acid.
2. The method of claim 1, wherein the ratio of the metal salt, ligand and solvent in the method of Fc-MOF precursor preparation is 1 (mmol): 1 (mmol): 5-20 (mL); in the solvent, the volume ratio of the N, N-dimethylformamide to the deionized water is 2:1.
3. the method according to claim 1, wherein when the non-metal source material is air, the method comprises: placing the Fc-MOF precursor in the center of a temperature zone of a high-temperature tubular furnace, setting the temperature of the high-temperature tubular furnace to be 500-800 ℃ in an air atmosphere, and reacting for 1-4 h at constant temperature to obtain the transition metal oxide nano heterojunction.
4. The method according to claim 1, wherein when the non-metal source material is a phosphorus source material, the method comprises: placing an Fc-MOF precursor at the center of a temperature zone of a high-temperature tubular furnace, placing a phosphorus source material at the upstream of the gas, setting the temperature of the high-temperature tubular furnace to be 300-600 ℃ under an inert atmosphere, and reacting for 1-4 h at constant temperature 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.
5. The method for preparing a two-component nano heterojunction material with coherent growth characteristics as claimed in claim 1, wherein when the non-metal source material is a sulfur source material, the method for preparing the two-component nano heterojunction material with coherent growth characteristics comprises: placing an Fc-MOF precursor at the center of a temperature zone of a high-temperature tubular furnace, placing a sulfur source material at the upstream of the gas, setting the temperature of the high-temperature tubular furnace to be 300-700 ℃ under an inert atmosphere, and reacting at constant temperature for 1-4 h to obtain a transition metal sulfide nano heterojunction;
the sulfur source material is selected from: sulfur powder and thiourea;
the mass ratio of the Fc-MOF precursor to the sulfur source material is 1:10 to 50.
6. The method for preparing a bi-component nano heterojunction material with coherent growth characteristics of claim 1, wherein when the non-metal source material is selenium powder, the method for preparing the bi-component nano heterojunction material with coherent growth characteristics comprises the following steps: placing an Fc-MOF precursor at the center of a temperature zone of a high-temperature tube furnace, placing selenium powder at the upstream of the gas, setting the temperature of the high-temperature tube furnace to be 300-500 ℃ under inert atmosphere, and reacting at constant temperature 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 according to claim 1, wherein when the non-metal source material is ammonia, the method comprises: placing the Fc-MOF precursor in the center 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 be 300-500 ℃ under the protection of inert atmosphere, and reacting for 1-4 h at constant temperature 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 bi-component nano-heterojunction material with coherent growth characteristics as claimed in claim 8 as an electrocatalyst in oxygen evolution reactions under alkaline conditions.
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