CN110624607B - In-situ grown two-dimensional conductive metal organic compound array - Google Patents
In-situ grown two-dimensional conductive metal organic compound array Download PDFInfo
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- 150000002902 organometallic compounds Chemical class 0.000 title claims abstract description 48
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 23
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
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- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
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- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 7
- 238000001075 voltammogram Methods 0.000 description 6
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 5
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
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- 238000000593 microemulsion method Methods 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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Abstract
The invention discloses a two-dimensional conductive metal organic compound array growing in situ, which comprises a three-dimensional substrate used as a carrier and a two-dimensional conductive nanosheet array growing in situ on the three-dimensional substrate, and comprises the following steps: dissolving a 2, 5-thiophenedicarboxylic acid ligand in ethanol; placing the three-dimensional substrate in the solution, and reacting in a closed container; and washing and drying the obtained product to obtain the array. The material obtained by the method does not need an additional metal source, is provided by a foam substrate, has excellent conductivity and a regularly arranged two-dimensional array structure, can effectively carry out charge and substance transmission, and has wide application prospects in the fields of energy, catalysis and the like.
Description
Technical Field
The invention relates to an in-situ grown nano material, in particular to an in-situ grown two-dimensional conductive metal organic compound array, belonging to the field of nano material preparation.
Background
In recent years, severe environmental issues and climate change have created an urgent need for the development of clean, renewable energy sources. The water electrolysis technology can convert electric energy generated by solar energy, wind energy and the like into hydrogen for large-scale storage, and lays a foundation for the wide utilization of renewable energy sources. However, current water electrolysis techniques present some important challenges: high overpotential, noble metal catalysts, and poor electrode stability, among others. Therefore, there is a need to develop new efficient, low cost and stable catalysts to facilitate large scale application of water electrolysis technology.
Metal is provided withThe organic compound is a novel electrochemical active material, is constructed by connecting metal ions and organic ligands, has the advantages of porosity, adjustable structure, high surface area and the like, and has the characteristics of inorganic and organic structural units on the molecular level, so that the organic compound shows wide application prospect. However, conventional bulk organometallic compounds have poor conductivity (-10) -10 S m -1 ) And a small pore size (less than 2 nm), and is generally prepared in a powder form, which is very disadvantageous in charge and material transfer, and thus is considered to be an electrochemical catalyst having poor performance.
Generally, there are various methods for synthesizing metal organic compounds, mainly including hydrothermal method, microwave method, diffusion method, ultrasonic method, template method, microemulsion method, coprecipitation method, etc. However, different synthesis methods and experimental conditions all affect the coordination mode of the metal and the organic ligand, the crystal nucleation growth and the self-assembly process, so that products with different structures and appearances are obtained. Among them, the solvothermal method is a common method for preparing metal organic compounds due to its simple operation, but in order to increase a certain parameter or to control the microstructure, surfactants, inhibitors, etc., which are difficult to remove, generally need to be added. However, to date, no report has been made on the preparation of in situ grown two-dimensional conductive metal organic compound arrays.
Disclosure of Invention
The invention aims to provide a method for growing a two-dimensional conductive metal organic compound array in situ.
The technical solution for realizing the purpose of the invention is as follows:
an in-situ grown two-dimensional conductive metal organic compound array comprises a three-dimensional substrate used as a carrier and a two-dimensional conductive nanosheet array grown in situ on the three-dimensional substrate, wherein,
when the three-dimensional substrate is foamed nickel, the conductive nanosheets are metal organic compound nanosheets of nickel and 2, 5-thiophenedicarboxylic acid;
when the three-dimensional substrate is foam iron, the conductive nanosheets are metal organic compound nanosheets of iron and 2, 5-thiophenedicarboxylic acid;
when the three-dimensional substrate is foam copper, the conductive nanosheets are metal organic compound nanosheets of copper and 2, 5-thiophenedicarboxylic acid.
When the three-dimensional substrate is foam ferronickel, the conductive nanosheets are metal organic compound nanosheets of bimetallic nickel and iron and 2, 5-thiophenedicarboxylic acid.
Preferably, the conductivity of the conductive nanosheet is from 21 to 33S m -1 。
A method for growing a two-dimensional conductive metal organic compound array in situ, comprising the steps of:
dissolving a 2, 5-thiophenedicarboxylic acid ligand in ethanol;
placing the three-dimensional substrate in the solution obtained in the step one, and reacting in a closed container;
and step three, washing and drying the obtained product to obtain the in-situ growth two-dimensional conductive metal organic compound array material.
Preferably, the reaction temperature is 100-150 DEG C o C, the time is 6-72 h.
Preferably, at 2 x 2.8cm 2 Based on the three-dimensional substrate of (1 mg mL) -1 The above 2, 5-thiophenedicarboxylic acid ligand.
An application of in-situ grown two-dimensional conductive metal organic compound array in the field of electrocatalytic reaction.
The electrocatalytic reaction comprises an oxygen evolution reaction, a hydrogen evolution reaction and a total hydrolysis reaction.
Compared with the prior art, the invention has the advantages that: (1) the method is suitable for different three-dimensional substrates, and is a universal synthesis method of a two-dimensional conductive metal organic compound array; (2) the obtained material has better conductivity, and overcomes the defect of poor conductivity of the traditional metal organic compound array; (3) the three-dimensional framework structure of the substrate is well utilized, the formation of a two-dimensional array is facilitated, meanwhile, the array structure is beneficial to material transmission, the ultrathin two-dimensional structure is prone to exposing more active sites, and excellent electrocatalytic total hydrolysis activity is shown; (4) the synthesis does not need to add extra metal source, the used raw materials are cheap and easy to obtain, and materials such as surfactant and the like do not need to be added, so that the environment pollution is avoided.
Drawings
FIG. 1 is a schematic diagram of the synthesis route of the two-dimensional conductive metal organic compound array grown in situ according to the present invention.
FIG. 2 is a scanning electron microscope (a) and a distribution diagram (b-f) of elements of an in-situ grown nickel two-dimensional conductive metal organic compound array prepared in example 1 of the present invention.
FIG. 3 is a field emission scanning electron microscope image of in-situ grown two-dimensional conductive metal organic compound arrays prepared in examples 2 (a) and 3 (b) of the present invention.
FIG. 4 is a field emission scanning electron micrograph of in situ grown two-dimensional conductive organometallic compound arrays prepared in examples 4 (a), 5 (b), 6 (c), and 7 (d) of the present invention.
FIG. 5 is an X-ray diffraction pattern (a) and a Fourier transform infrared spectrum (b) of an in-situ grown nickel two-dimensional conductive organometallic array prepared in accordance with example 1 of the present invention.
FIG. 6 is a graph of the performance of in-situ grown two-dimensional conducting MOFs prepared in examples 1, 2,5 and 7 of the present invention, wherein (a) is the linear sweep voltammogram of the oxygen evolution reaction, and (b) is the linear sweep voltammogram of the hydrogen evolution reaction.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples.
With reference to fig. 1, the invention prepares an in-situ growth two-dimensional conductive metal organic compound array according to the following steps:
step one, dissolving a 2, 5-thiophenedicarboxylic acid ligand in ethanol, wherein the adding concentration of the 2, 5-thiophenedicarboxylic acid ligand is 1mg mL -1 The above;
step two, placing the three-dimensional substrate (foamed nickel, foamed copper, foamed iron and foamed nickel iron) in the solution obtained in the step one at the temperature of 100-150 DEG C o Reacting for 6-72 h in a closed container at the temperature of C;
and step three, washing and drying the obtained product to obtain the in-situ growth two-dimensional conductive metal organic compound array material.
The present invention will be described in further detail with reference to specific embodiments.
Example 1:
the method comprises the following steps: dissolving 50mg of 2, 5-thiophenedicarboxylic acid ligand in 30mL of ethanol;
step two: adding foamed nickel into the solution obtained in the step one, and placing the mixture in a closed container 150 o C, reacting for 12 hours;
step three: washing the obtained product with ethanol twice, washing the product with deionized water twice, and freeze-drying to obtain the in-situ grown nickel two-dimensional conductive metal organic compound array material.
The field emission scanning electron microscope image and the element distribution diagram of the obtained in-situ grown nickel two-dimensional conductive metal organic compound array are shown in fig. 2, which shows that the material is an ultrathin two-dimensional array, and all elements are uniformly distributed. The X-ray diffraction pattern is shown in FIG. 5 (a), indicating that it is a polycrystal; fourier transform Infrared Spectroscopy (1561 cm) as shown in FIG. 5 (b) -1 The peaks in (A) are due to the antisymmetric stretching of the carboxylate groups in the in-situ grown nickel two-dimensional conductive organometallic compound, 1521 and 1363 cm -1 The peaks at (a) are due to the characteristic tensile vibrations of the carboxylate groups and, in combination with the X-ray diffraction pattern and the elemental species in the elemental profile, indicate that the metal-organic compound was prepared. The results of the conductivity test are shown in Table 1, and the conductivity is 25-33S m -1 Indicating that it has better conductivity. The voltammograms for oxygen evolution and hydrogen evolution reactions are shown in FIGS. 6 (a, b) at a current density of 10mA cm -2 Overpotentials at the time of the reaction were 282mV (oxygen evolution reaction) and 137mV (hydrogen evolution reaction), respectively; the lower overpotential of the compound shows that the compound has better application prospect in the field of electrocatalysis.
Example 2:
the method comprises the following steps: dissolving 50mg of 2, 5-thiophenedicarboxylic acid ligand in 30mL of ethanol;
step two: adding foamed iron into the solution obtained in the step one, and placing the mixture in a closed container 150 o C, reacting for 12 hours;
step three: washing the obtained product with ethanol twice, washing the product with deionized water twice, and freeze-drying to obtain the in-situ grown nickel two-dimensional conductive metal organic compound array material.
The field emission scanning electron microscope image of the obtained in-situ grown iron two-dimensional conductive metal organic compound array is shown in fig. 3 (a), which shows that the material is an ultrathin two-dimensional array. The conductivity of the conductive coating is 22 to 31S m -1 In between. The voltammograms for oxygen evolution and hydrogen evolution reactions are shown in FIGS. 6 (a, b) at a current density of 10mA cm -2 The overpotential of the reaction was 263mV (oxygen evolution reaction) and 116mV (hydrogen evolution reaction), respectively;
example 3:
the method comprises the following steps: dissolving 50mg of 2, 5-thiophenedicarboxylic acid ligand in 30mL of ethanol;
step two: adding the foamy copper into the solution obtained in the first step, and 150 percent in a closed container o C, reacting for 12 hours;
step three: washing the obtained product with ethanol twice, washing the product with deionized water twice, and freeze-drying to obtain the in-situ grown nickel two-dimensional conductive metal organic compound array material.
The field emission scanning electron microscope image of the obtained in-situ grown copper two-dimensional conductive metal organic compound array is shown in fig. 3 (b), which shows that the material is an ultrathin two-dimensional array. The conductivity of the conductive coating is 21 to 29S m -1 In the meantime.
Example 4:
the method comprises the following steps: dissolving 50mg of 2, 5-thiophenedicarboxylic acid ligand in 30mL of ethanol;
step two: adding foamed nickel iron with 20% iron content into the solution obtained in the step one, and placing in a closed container for 150% o C, reacting for 12 hours;
step three: washing the obtained product with ethanol twice, washing the product with deionized water twice, and freeze-drying to obtain the in-situ grown nickel two-dimensional conductive metal organic compound array material.
The field emission scanning electron microscope image of the obtained in-situ grown ferronickel bimetallic (foamed ferronickel with 20% iron content is used as a substrate) two-dimensional conductive metal organic compound array is shown in fig. 4 (a), which shows that the material is an ultrathin two-dimensional array.
Example 5:
the method comprises the following steps: dissolving 50mg of 2, 5-thiophenedicarboxylic acid ligand in 30mL of ethanol;
step two: adding 40% iron content foamed nickel iron into the solution obtained in step one, and placing in a closed container 150% o C, reacting for 12 hours;
step three: washing the obtained product with ethanol twice, washing the product with deionized water twice, and freeze-drying to obtain the in-situ grown nickel two-dimensional conductive metal organic compound array material.
The field emission scanning electron microscope image of the obtained in-situ grown ferronickel bimetallic (40% iron content foamed ferronickel is used as the substrate) two-dimensional conductive metal organic compound array is shown in fig. 4 (b), which shows that the material is an ultrathin two-dimensional array. The voltammograms for oxygen evolution and hydrogen evolution reactions are shown in FIGS. 6 (a, b) at a current density of 10mA cm -2 The overpotentials during the reaction were 243mV (oxygen evolution reaction) and 158mV (hydrogen evolution reaction), respectively;
example 6:
the method comprises the following steps: dissolving 50mg of 2, 5-thiophenedicarboxylic acid ligand in 30mL of ethanol;
step two: adding foamed nickel iron with 60% iron content into the solution obtained in the step one, and placing in a closed container for 150% o C, reacting for 12 hours;
step three: washing the obtained product with ethanol twice, washing the product with deionized water twice, and freeze-drying to obtain the in-situ grown nickel two-dimensional conductive metal organic compound array material.
The field emission scanning electron microscope image of the obtained in-situ grown ferronickel bimetallic (foamed ferronickel with 60% iron content is used as a substrate) two-dimensional conductive metal organic compound array is shown in fig. 4 (c), which shows that the material is an ultrathin two-dimensional array.
Example 7:
the method comprises the following steps: dissolving 50mg of 2, 5-thiophenedicarboxylic acid ligand in 30mL of ethanol;
step two: adding 80% iron content foamed nickel iron into the solution obtained in step one, and placing in a closed container 150% o C, reacting for 12 hours;
step three: washing the obtained product with ethanol twice, washing the product with deionized water twice, and freeze-drying to obtain the in-situ grown nickel two-dimensional conductive metal organic compound array material.
The field emission scanning electron microscope image of the obtained in-situ grown ferronickel bimetal (foamed ferronickel with 80% of iron content is taken as a substrate) two-dimensional conductive metal organic compound array is shown in fig. 4 (d), which shows that the material is an ultrathin two-dimensional array. The voltammograms for oxygen evolution and hydrogen evolution reactions are shown in FIGS. 6 (a, b) at a current density of 10mA cm -2 The overpotential for the reaction was 250mV (oxygen evolution reaction) and 190mV (hydrogen evolution reaction), respectively.
Claims (6)
1. The in-situ grown two-dimensional conductive metal organic compound array is characterized by comprising a three-dimensional substrate used as a carrier and a two-dimensional conductive nanosheet array grown in situ on the three-dimensional substrate, wherein the conductivity of the conductive nanosheet is 21-33 S.m -1 (ii) a Wherein the content of the first and second substances,
when the three-dimensional substrate is foamed nickel, the conductive nanosheets are metal organic compound nanosheets of nickel and 2, 5-thiophenedicarboxylic acid;
when the three-dimensional substrate is foamed iron, the conductive nanosheets are metal organic compound nanosheets of iron and 2, 5-thiophenedicarboxylic acid;
when the three-dimensional substrate is foam copper, the conductive nanosheets are metal organic compound nanosheets of copper and 2, 5-thiophenedicarboxylic acid;
when the three-dimensional substrate is foam ferronickel, the conductive nanosheets are metal organic compound nanosheets of bimetallic nickel and iron and 2, 5-thiophenedicarboxylic acid;
the preparation method comprises the following steps:
dissolving a 2, 5-thiophenedicarboxylic acid ligand in ethanol to obtain a mixed solution;
placing the three-dimensional substrate in the mixed solution obtained in the step one, and reacting in a closed container;
and step three, washing and drying the obtained product to obtain the in-situ growth two-dimensional conductive metal organic compound array material.
2. The method of making an array of claim 1, comprising the steps of:
dissolving a 2, 5-thiophenedicarboxylic acid ligand in ethanol to obtain a mixed solution;
placing the three-dimensional substrate in the mixed solution obtained in the step one, and reacting in a closed container;
and step three, washing and drying the obtained product to obtain the in-situ growth two-dimensional conductive metal organic compound array material.
3. The method of claim 2, wherein the reaction temperature is 100 to 150 ℃ o C, the time is 6-72 h.
4. The method of claim 2, wherein the concentration is 2 x 2.8cm 2 Based on the three-dimensional substrate of (1 mg. multidot.mL) -1 The above 2, 5-thiophenedicarboxylic acid ligand.
5. Use of the array of claim 1 in the field of electrocatalytic reactions.
6. The use according to claim 5, wherein the electrocatalytic reaction comprises an oxygen evolution reaction, a hydrogen evolution reaction.
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