CN113817175B - Preparation method and application of one-dimensional chain-like Schiff base Mn-based coordination polymer - Google Patents
Preparation method and application of one-dimensional chain-like Schiff base Mn-based coordination polymer Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a one-dimensional chain-like Schiff base Mn-based coordination polymer, belonging to the technical field of coordination chemistry. 3-ethoxy salicylaldehyde ethanolamine Schiff base ligand and metal Mn are bridged and coordinated to form a one-dimensional chain structure; and is directly pyrolyzed into single valence state Mn under inert atmosphere 2+ O-Embedded porous carbon skeleton (Mn) 2+ O/C) composite material. The mass spectrum accurately tracks the pyrolysis process in real time, and the pyrolysis product is used as the lithium ion battery cathode material to carry out electrochemical performance test. The polymer of the invention has unique pyrolysis process, and the prepared pyrolysis product is 800mA g ‑1 The specific capacity of 470mAh g after circulating for 100 circles under the current density ‑1 And 1000mA g ‑1 Specific capacity under multiplying power is 310mAh g ‑1 . The one-dimensional chain coordination polymer and the pyrolysis product are expected to become novel energy storage materials.
Description
Technical Field
The invention belongs to the technical field of coordination chemistry, and relates to preparation and application of a one-dimensional chain-like Schiff base Mn-based coordination polymer.
Background
The multi-dimension from molecular, crystalline to nano-scale is the basis of chemical analysis of materials. The pyrolysis reaction is a process of material thermal decomposition, and is also one of methods for converting a precursor into an advanced nano material with a special structure and performance. The current research on metal-organic framework Materials (MOFs) that are more pyro-thermic is the classical material system for the research on pyrolysis processes. In recent years, the pyrolysis of metal-organic framework materials and simple organic-inorganic composite materials as precursors at appropriate temperatures has been an effective way to prepare electrode materials. And the precise regulation and control of the precursor structure are realized by means of controlling the quantity and the type of metal ions, the coordination geometrical configuration of the metal ions, the ligand configuration, the internal bridge ligand, the intra-cluster/intra-cluster interaction and the like.
However, the pyrolysis reaction is complex and difficult to predict, and the capture and process tracking of small molecules have certain difficulties, which hinder the research of the current pyrolysis process. Compared with three-dimensional MOFs, the 1D chain metal coordination polymer is a coupling structure of cluster compounds, wherein a metal core in a basic unit is coordinated with a plurality of ligands, and the ligands and the metal core of an adjacent unit form coordination to present a chain structure. Currently, there are significant challenges to understanding the pyrolysis process of 1D chain metal coordination polymers.
The Schiff base ligand mainly refers to an organic compound containing an imine (-CH-N-) or azomethine (-CR-N-) characteristic group. Schiff base complexes are widely used in the fields of catalysis, photochromism and energy storage due to their pyrolysis products having N, O coordination mode and the ability to stabilize three-dimensional metal ions. The designability of the structure is obviously superior to that of the traditional solid material. However, pyrolysis is an effective material treatment means to provide more diverse structural transformations to the Schiff base complexes. In addition, structurally unique ligands evolve into nitrogen-containing carbon materials during pyrolysis, and metal nuclei evolve into corresponding oxides embedded in the carbon materials. The composite material has excellent electrochemical performance due to the strong coupling effect between the metal oxide and the carbon base. In recent years, most researchers focus on the research on the pyrolysis and application of simple Schiff base complexes, and the research on the pyrolysis tracking and application of one-dimensional chain Schiff base metal coordination polymers is less reported.
Recently, Zeng investigated disalicylaldehyde o-phenylenediamine coordinated Mn 3 (Mn 3 (3-MeOsalo phen) 2 (Cl) 2 ) Clustering and direct pyrolysis to mixed valence MnO under inert atmosphere x Embedded porous N-doped carbon skeleton (MnO) x /C) composite materials. Combining with the thermogravimetric-mass spectrometry (TG-MS) and other characterization technologies, accurately tracking the pyrolysis process in real time, and deducing Mn in the product 2+ /Mn 3+ The ratio ensures excellent electrochemical performance. Sample MnO thereof x the/C-900 reached 943F/g at 1A/g, and the capacity retention after 5000 cycles was still 90% (Nano Research,2021,10.1007/s 12274-021-3481-1).
Based on the method, a well-designed coordination structure is searched, and the further research on the real-time tracking of the pyrolysis process is of great significance. The major challenge today comes from the specific decomposition and recombination reactions of the schiff base complexes at high temperatures, which undoubtedly increases the difficulty of tracking the entire formation process.
Therefore, designing a Schiff base complex with a specific structure as a precursor for exploring a pyrolysis process to obtain a pyrolysis material with a specific structure still needs an urgent structure-performance relationship between the connection chemistry and the material.
Disclosure of Invention
In order to deeply understand pyrolysis processes with different dimensions and the relationship between the structure and the performance, the invention aims to provide a one-dimensional chain-like Schiff base Mn-based coordination polymer, a pyrolysis product and application.
The invention provides a one-dimensional chain Schiff base Mn-based coordination polymer, which has the crystallographic data as follows: molecular formula is [ Mn (L) 2 CH 3 OH] n ·SCN n Molecular weight of 559.51 and crystallographic data of
α＝90.000(0)°，β＝98.839(4)°，γ＝90.000(0)°，
Z-4, monoclinic system, P2 1 A/n space group.
The repeating unit structure of the one-dimensional chain-like Schiff base Mn-based coordination polymer is as follows:
the one-dimensional chain Schiff base Mn-based coordination polymer is a one-dimensional chain metal organic coordination polymer formed by connecting a repeating unit shown in a formula 1 with a metal core Mn coordination chain of an adjacent unit through a hydroxyl on ethanolamine.
The unit structure of the one-dimensional chain-like Schiff base Mn-based coordination polymer is composed of 1 manganese ion, 2 molecules of 3-ethoxy salicylaldehyde ethanolamine and 1 molecule of methanol, and 1 free SCN molecule which does not participate in coordination exists. The manganese ions are symmetrically coordinated with 2 oxygen atoms and 2 nitrogen atoms from the 3-ethoxy salicylaldehyde ethanolamine molecule, and simultaneously, the oxygen atoms of the methanol molecule and the terminal oxygen atoms of the ethanolamine of an adjacent unit structure are also coordinated, so that the manganese ions are in a coordination environment of a hexa-coordinated distorted octahedron.
The one-dimensional chain-like Schiff base Mn-based coordination polymer has a special bridging coordination molecular structure, and shows a unique pyrolysis process in a high-temperature pyrolysis process due to the unique coordination structure. The bridging coordination characteristic of the 3-ethoxy salicylaldehyde ethanolamine ligand molecule is easy to develop into a three-dimensional porous carbon material in a final pyrolysate, and the transmission kinetics of ions and electrons can be remarkably improved. The mononuclear metal manganese is developed into a corresponding nano-scale metal oxide which is embedded in the three-dimensional porous carbon material and serves as a carrier for contributing capacity.
The invention also provides a preparation method of the one-dimensional chain Schiff base Mn-based coordination polymer, which comprises the following specific steps:
1. weighing 1-1.5mmol of 3-ethoxy salicylaldehyde ethanolamine ligand, dissolving in 10-15mL of methanol, dropwise adding 2-3 drops of tetramethyl ammonium hydroxide solution, stirring thoroughly, and preparing into solution A when the orange yellow color disappears.
2. Weighing 1-1.5mmol NaSCN and 0.6-1mmol Mn (OAC) 2 Heating and ultrasonic dissolving in 5-10mL of methanol to prepare solution B.
3. Adding the solution B into the solution A, fully stirring for 6-8h, uniformly mixing, filtering, placing the obtained filtrate into a beaker, sealing the opening of the beaker by using a punctured preservative film, and standing at room temperature for natural volatilization until black crystals are separated out.
4. And washing the obtained black crystal by methanol, filtering, and drying in vacuum at room temperature to obtain the one-dimensional chain Schiff base Mn-based coordination polymer.
The invention also provides a preparation method of the pyrolysis product of the one-dimensional chain Schiff base Mn-based coordination polymer, which comprises the following specific operations: heating the one-dimensional chain-like Schiff base Mn-based coordination polymer to 600-900 ℃ in a tubular furnace, maintaining for 2h, and calcining and pyrolyzing in an argon atmosphere to obtain a pyrolysis product.
Further, in the high-temperature pyrolysis process of the coordination polymer, mononuclear manganese metal is changed into corresponding nanoscale metal oxide and embedded in the three-dimensional porous carbon material.
The invention also provides application of the pyrolysis product of the one-dimensional chain-like Schiff base Mn-based coordination polymer in the lithium ion battery cathode material.
Further, the pyrolysis product is used as a high-performance lithium ion battery negative electrode material and is added at 800mA g -1 The specific capacity of 470mAh g after circulating for 100 circles under the current density -1 ，1000mA g -1 Specific capacity under multiplying power is 310mAh g -1 。
Advantageous effects of the invention
1. The one-dimensional chain Schiff base Mn-based coordination polymer takes 3-ethoxy salicylaldehyde ethanolamine Schiff base as a ligand to present a one-dimensional chain structureThe coordination polymer molecule has a special coordination environment, and the unique bridging coordination molecule structure enables the high-temperature pyrolysis process to show a unique pyrolysis process. The electrochemical performance test of the pyrolysis product as the lithium ion battery cathode material shows that: at 800mA g -1 The specific capacity of 470mAh g after circulating for 100 circles under the current density -1 About, and 1000mA g -1 Specific capacity under multiplying power is 310mAh g -1 Left and right.
2. In the pyrolysis tracking process, the invention finds that the unique bridging coordination molecular structure and the breakage of the coordination bond are accompanied with the dissociation of a one-dimensional chain structure and form a coordination-lacking mononuclear cluster. And the unbroken (phenyl) C-O-Mn-O-C (phenyl) bond will form a specific Mn at a later stage 2+ The O-oxide is embedded in the porous carbon network. The mosaic structure can obviously improve the transport kinetics of ions and electrons, and further shows excellent electrochemical performance.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of a structural unit of a one-dimensional chain-like Schiff base Mn-based coordination polymer prepared by the invention;
FIG. 2 is a one-dimensional chain diagram of a one-dimensional chain-like Schiff base Mn-based coordination polymer adopted by the invention;
FIG. 3 is an XRD pattern of pyrolysis products of one-dimensional chain-like Schiff base Mn-based coordination polymer adopted by the invention at different temperatures;
FIG. 4 is a TG plot of the thermogravimetric trace of a one-dimensional chain-like Schiff base Mn-based coordination polymer employed in the present invention;
FIG. 5 is a mass spectrum of a pyrolysis trace of a one-dimensional chain-like Schiff base Mn-based coordination polymer employed in the present invention;
FIG. 6 is an SEM image of a one-dimensional chain-like Schiff base Mn-based coordination polymer employed in the present invention;
FIG. 7 shows that the pyrolysis product of the one-dimensional chain-like Schiff base Mn-based coordination polymer adopted by the invention is assembled into a battery at 800mA g -1 A plot of cycling performance at current density;
FIG. 8 is a graph of rate capability at different current densities after the pyrolysis products of the one-dimensional chain-like Schiff base Mn-based coordination polymer adopted by the invention are assembled into a battery.
Detailed Description
The present invention will be described in detail below with reference to examples and the accompanying drawings so that the present invention may be understood by researchers, but the scope of the present invention is not limited to the following examples.
The one-dimensional chain-like Schiff base Mn-based coordination polymer illustrated in this example: molecular formula is [ Mn (L) 2 CH 3 OH] n -·SCN n Molecular weight of 559.51 and crystallographic data of
α＝90.000(0)°,β＝98.839(4)°,γ＝90.000(0)°，
Z-4, monoclinic system, P2 1 A/n space group.
The one-dimensional chain Schiff base Mn-based coordination polymer is a one-dimensional chain metal organic coordination polymer which is formed by connecting a repeating unit shown in a formula 1 with a metal core Mn coordination chain of an adjacent unit through a hydroxyl on ethanolamine.
The unit structure of the one-dimensional chain-like Schiff base Mn-based coordination polymer is composed of 1 manganese ion, 2 molecules of 3-ethoxy salicylaldehyde ethanolamine and 1 molecule of methanol, and 1 free SCN molecule which does not participate in coordination exists. The manganese ions are symmetrically coordinated with 2 oxygen atoms and 2 nitrogen atoms from the 3-ethoxy salicylaldehyde ethanolamine molecule, and simultaneously, the oxygen atoms of the methanol molecule and the terminal oxygen atoms of the ethanolamine of an adjacent unit structure are also coordinated, so that the manganese ions are in a coordination environment of a hexa-coordinated distorted octahedron. The one-dimensional chain-like Schiff base Mn-based coordination polymer has a special bridging coordination molecular structure, and shows a unique pyrolysis process in a high-temperature pyrolysis process due to the unique coordination structure. The bridging coordination characteristic of the 3-ethoxy salicylaldehyde ethanolamine ligand molecule is easily developed into a three-dimensional porous carbon material in a final pyrolysate, and the transmission kinetics of ions and electrons can be remarkably improved. The mononuclear metal manganese evolved into a corresponding nanoscale metal oxide embedded in a three-dimensional porous carbon material as a capacity-contributing carrier.
The invention provides a preparation method of a one-dimensional chain-like Schiff base Mn-based coordination polymer, a pyrolysis process tracking method and application of a pyrolysate in energy storage of a lithium ion battery.
Example 1
Weighing 1mmol of 3-ethoxy salicylaldehyde ethanolamine ligand, placing in a 100mL round-bottom flask, adding 10mL of organic solvent methanol, magnetically stirring for dissolving, dropwise adding 2 drops of tetramethyl ammonium hydroxide solution, stirring for 20min, and preparing to obtain solution A when the orange yellow color disappears.
Weighing 1mmol NaSCN and 0.6mmol Mn (OAc) 2 The mixture was placed in a 25mL beaker and dissolved in 5mL of methanol by heating and ultrasonic treatment to prepare a solution B.
Solution B was added rapidly to solution A and stirring was continued for 6 h. And after uniform mixing, filtering the obtained mixed solution, placing the filtrate in a 25mL beaker, sealing the opening of the beaker by using an empty preservative film, and naturally volatilizing for 5 days at room temperature to obtain large black crystals with good crystallinity.
Washing the obtained black crystals with methanol, filtering, and drying in vacuum at room temperature to obtain the one-dimensional chain Schiff base Mn-based coordination polymer crystals.
The X-ray single crystal diffraction test and data analysis of the bulk black crystal obtained in this example showed that: the molecular formula of the obtained polymer is [ Mn (L) ] 2 CH 3 OH] n ·SCN n Molecular weight of 559.51 and crystallographic data of
α＝90.000(0)°，β＝98.839(4)°，γ＝90.000(0)°，
Z is 4, monoOrthorhombic system, P2 1 A/n space group. The schematic diagram of the crystal structure of the structural unit of the one-dimensional chain Schiff base Mn-based coordination polymer is shown in figure 1, and the schematic diagram of the one-dimensional chain crystal structure is shown in figure 2.
The one-dimensional chain-like Schiff base Mn-based coordination polymer crystal is calcined and pyrolyzed in a tubular furnace at the temperature of 600-900 ℃ for 2h under the argon atmosphere to obtain a pyrolysis product.
From XRD in FIG. 3, the pyrolysis product is Mn 2+ An O/carbon composite. Amorphous carbon is converted to graphitized carbon at 900 deg.C, while Mn 2+ The O compound is not oxidized to a higher manganese compound.
The pyrolysis process of the chain-like Schiff base Mn-based coordination polymer is accurately tracked in real time by utilizing a TG-MS technology, and the pyrolysis process of the chain-like Schiff base Mn-based coordination polymer is researched on a one-dimensional scale. Research has shown that the overall pyrolysis process can be divided into three stages: (i) escape of ligand molecules; (ii) (ii) cleavage of coordination bonds; (iii) complete decomposition of the ligand. As can be seen from the combination of fig. 4 and 5, the fragment escape and weight loss of the ligand molecule are consistent, so the pyrolysis process can be divided into three parts: detection of CH from room temperature to 130 deg.C 3 + (m/z 15) and CH 3 O - (m/z-31) fragments, the TG curve shows significant weight loss. Specifically, in one aspect, cleavage of a methyl group on a methylene group produces CH 3 + On the other hand, the coordinate bond formed by the methanol molecule at this time is broken to generate CH 3 O - . CH was detected when the temperature rose from 190 ℃ to 550 ℃ 3 CH 2 O - (m/z＝45),CH 2 CH 2 N + (m/z 42) fragments, CH corresponding to 190 ℃ to 290 ℃ 3 CH 2 O - The escape of (a) can be attributed to the cleavage of ether bonds on the ligand molecule. It is noted that there is always CH in the range from 190 ℃ to 550 ℃ 2 CH 2 N + Due to the cleavage of the ethanolamine to form a coordination bond, and accompanied by dissociation of a one-dimensional chain structure. Most particularly, C was not detected 6 H 6 Molecular, meaning that the (phenyl) C-O-Mn-O-C (phenyl) bond is not broken and forms a specific Mn at a later stage 2+ O-oxide inlaid in porousIn the carbon network, as shown in fig. 6. The most specific pyrolysis process consists in the formation of Mn 2+ O is embedded in the structure of the porous carbon network, thereby protecting Mn at higher temperature 2+ Oxidized to higher manganese.
Electrochemical performance tests show that (fig. 7 and 8), the pyrolysis product is used as the negative electrode material of the lithium ion battery and has a voltage window of 0.01-3.0V (vs + ) Has excellent long circulation performance and good high rate performance at 800mA g -1 The specific capacity of 470mAh g after circulating for 100 circles under the current density -1 About, and 1000mA g -1 Specific capacity under multiplying power is 310mAh g -1 Left and right.
Example 2
Weighing 1.3mmol of 3-ethoxy salicylaldehyde ethanolamine ligand, placing in a 100mL round-bottom flask, adding 10mL of organic solvent methanol, magnetically stirring for dissolving, dropwise adding 2 drops of tetramethyl ammonium hydroxide solution, stirring for 20min, and preparing to obtain solution A when the orange yellow color disappears.
Weighing 1.2mmol NaSCN and 1mmol Mn (OAc) 2 The mixture was placed in a 25mL beaker and dissolved in 10mL of methanol by heating and ultrasonic treatment to prepare a solution B.
Solution B was added rapidly to solution A and stirring was continued for 7 h. And after uniform mixing, filtering the obtained mixed solution, placing the filtrate in a 25mL beaker, sealing the opening of the beaker by using an empty preservative film, and naturally volatilizing for 6 days at room temperature to obtain large black crystals with good crystallinity.
Washing the obtained black crystals with methanol, filtering, and drying in vacuum at room temperature to obtain the one-dimensional chain Schiff base Mn-based coordination polymer crystals. The crystal structure and the respective characteristics were the same as in example 1.
Example 3
Weighing 1.5mmol of 3-ethoxy salicylaldehyde ethanolamine ligand, placing in a 100mL round-bottom flask, adding 15mL of organic solvent methanol, magnetically stirring for dissolving, dropwise adding 3 drops of tetramethyl ammonium hydroxide solution, stirring for 20min, and preparing to obtain solution A when the orange yellow color disappears.
Weighing 1.5mmol NaSCN and 1mmol Mn (OAc) 2 Placing in a 25mL beaker, heating and ultrasonic dissolving in 10mL nailAnd (5) preparing alcohol to obtain a solution B.
Solution B was added rapidly to solution A and stirring was continued for 8 h. And after uniform mixing, filtering the obtained mixed solution, placing the filtrate in a 25mL beaker, sealing the opening of the beaker by using an empty preservative film, and naturally volatilizing for 7 days at room temperature to obtain large black crystals with good crystallinity.
Washing the obtained black crystals with methanol, filtering, and drying in vacuum at room temperature to obtain the one-dimensional chain Schiff base Mn-based coordination polymer crystals. The resulting crystal structure and various characterizations were the same as in example 1.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A one-dimensional chain-like Schiff base Mn-based coordination polymer is characterized in that: the molecular formula of the coordination polymer is [ Mn (L) 2 CH 3 OH] n ·SCN n L is 3-ethoxy salicylaldehyde ethanolamine with molecular weight of 559.51 and crystallographic data of
α＝90.000(0)°，β＝98.839(4)°，γ＝90.000(0)°，
Z-4, monoclinic system, P2 1 A/n space group.
2. The one-dimensional chain-like schiff base Mn-based coordination polymer according to claim 1, wherein: the hydroxyl on the ethanolamine is linked with the metal core Mn of the adjacent unit in a coordination way to form a one-dimensional chain-shaped metal-organic coordination polymer.
3. The method for producing a pyrolysis product of a one-dimensional chain-like schiff base Mn-based coordination polymer according to claim 1, wherein: heating the one-dimensional chain-like Schiff base Mn-based coordination polymer to 600-900 ℃ in a tubular furnace, keeping for 2h, and calcining and pyrolyzing in an argon atmosphere to obtain a pyrolysis product.
4. The pyrolysis product of a one-dimensional chain-like schiff base Mn-based coordination polymer according to claim 1, wherein: in the high-temperature pyrolysis process of the coordination polymer, mononuclear manganese metal is changed into corresponding nanoscale metal oxide which is embedded in a three-dimensional porous carbon material.
5. The use of the pyrolysis product of claim 4 in a negative electrode material for a lithium ion battery, wherein: in the pyrolysis process of the coordination polymer, the pyrolysis product of the nano metal oxide embedded in the three-dimensional porous carbon material is a high-performance lithium ion battery cathode material.
6. The use of the pyrolysis product of claim 5 in a negative electrode material for a lithium ion battery, wherein: at 800mA g -1 The specific capacity of 470mAh g after circulating for 100 circles under the current density -1 ，1000mA g -1 Specific capacity under multiplying power is 310mAh g -1 。
7. The method for preparing a one-dimensional chain-like schiff base Mn-based coordination polymer according to claim 1, comprising the steps of:
(1) weighing 1-1.5mmol of 3-ethoxy salicylaldehyde ethanolamine ligand, dissolving in 10-15mL of methanol, dropwise adding 2-3 drops of tetramethyl ammonium hydroxide solution, stirring fully, and preparing into solution A when the orange color disappears;
(2) weighing 1-1.5mmol NaSCN and 0.6-1mmol Mn (OAc) 2 Heating and ultrasonically dissolving the mixture in 5-10mL of methanol to prepare a solution B;
(3) adding the solution B into the solution A, fully stirring and uniformly mixing, filtering, placing the obtained filtrate into a beaker, sealing the opening of the beaker by using a perforated preservative film, and placing the beaker at room temperature for natural volatilization until black crystals are separated out;
(4) and washing the obtained black crystals with methanol, filtering, and drying in vacuum at room temperature to obtain the one-dimensional chain Schiff base Mn-based coordination polymer.
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