CN113773493B - Preparation method of phthalocyanine-based two-dimensional organic framework material ultrathin nanobelt - Google Patents
Preparation method of phthalocyanine-based two-dimensional organic framework material ultrathin nanobelt Download PDFInfo
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Abstract
The invention relates to the field of preparation of Organic ultrathin nano materials, in particular to a synthesis method of an amide-linked phthalocyanine-based two-dimensional Covalent Organic Frameworks (COFs) material ultrathin nanobelt. The ultra-thin nano-belt material of phthalocyanine group two-dimensional COF material is obtained by using Cu (TAPc) and p-phenylenediamine as basic building units under the condition of the existence of a large amount of p-tert-butyl aniline. The ultra-thin nanobelt of the phthalocyanine-based two-dimensional COF material prepared by the synthesis method has high orderliness, the length is about 20 microns at the longest, the width is about 50nm at the minimum, the thickness is about 5nm at the thinnest, and the length, the width and the thickness can be adjusted by changing the amount of the adjusting agent. The method has good universality and can be used for synthesizing a plurality of ultra-thin nanobelt materials of phthalocyanine-based two-dimensional COF materials with different functional properties. The preparation method has the advantages of simple process, easily controlled synthesis conditions, high product yield, easy purification and separation, and easy realization of industrial production.
Description
Technical Field
The invention relates to the field of preparation of Organic ultrathin nano materials, in particular to a synthesis method of an amide-linked phthalocyanine-based two-dimensional Covalent Organic Frameworks (COFs) material ultrathin nanobelt.
Background
Covalent Organic Frameworks (COFs) are a novel class of Organic porous crystalline materials, which are formed by constructing monomers from small Organic moleculesThe elements are connected by covalent bonds according to a certain geometrical topological structure. The two-dimensional conjugated COFs material has a highly conjugated pi electronic structure, is a very potential semiconductor material, and has very wide application prospects in the fields of optoelectronic devices, chemical sensing devices, photoelectrocatalysis and the like. Phthalocyanine is a rigid compound with a stable 18 pi electron conjugated system, and is an excellent building unit of two-dimensional conjugated COFs materials. The two-dimensional conjugated COFs material constructed by phthalocyanine molecules has high stability and good electron transmission performance, and shows excellent performance in aspects of electrocatalytic carbon dioxide reduction, gas sensing detection and the like. For example, Jiang et al have constructed two examples of two-dimensional conjugated COFs materials with Co (TAPc) and p-phenylenediamine and biphenyldiamine, respectively, and the conductivities of the two examples of two-dimensional conjugated COFs materials reach 3.7 × 10-3And 1.6X 10-3S m-1The selectivity of electrocatalytic carbon dioxide reduction can reach 97%, continuous electrolysis can be carried out for 40h under-0.70V and the stability is kept, and the conversion frequency of a single catalytic site reaches 2.2s-1And the excellent electrocatalytic carbon dioxide reduction performance is shown. Mirica et al construct phthalocyanine group COFs for pyrazine ring remuneration from octa-amino phthalocyanine and pyrene tetrone. The COF material has a conductivity of 2.51 × 10-3S/m, and after doping by I2, the conductivity is further improved and it is resistant to oxidizing gases (NO and NO)2) And a reducing gas (NH)3And H2S) generally shows excellent corresponding performance, and shows that the phthalocyanine-based two-dimensional conjugated COF material has wide application prospect in the aspect of gas sensing devices.
However, in order to fully exert the performance advantages of the phthalocyanine-based two-dimensional conjugated COF material, the morphology of the material needs to be controlled. Jiang et al, by introducing a mono-amino regulator in the synthesis of two-dimensional imino COFs, synthesize a two-dimensional COFs nanosheet with an ultrathin structure and show ultrahigh photocatalytic performance.
Disclosure of Invention
The invention relates to a synthesis method of an amide-linked phthalocyanine-based two-dimensional organic framework material ultrathin nanobelt. In the process of preparing the phthalocyanine-based two-dimensional conjugated COFs by using Cu (TAPc), p-phenylenediamine, biphenyldiamine and other linear aromatic diamines as basic building units, a large amount of p-tert-butyl aniline is introduced as a steric hindrance regulator to control the growth of the COFs, so that the one-dimensional ultrathin nano-belt structure of the phthalocyanine-based COFs material is obtained.
A preparation method of an ultrathin nanobelt made of a phthalocyanine-based two-dimensional organic framework material is characterized by comprising the following specific steps:
step 1: dissolving Cu (TAPc), p-phenylenediamine and p-tert-butylamine in a mixed solvent of N-methyl pyrrolidone and n-butyl alcohol according to the molar weight ratio (1:2-2.1:40-45), wherein the sum of the total mass of three ligands added in each milliliter of the mixed solvent is 20-50 mg, and then transferring the mixed solvent into a high-pressure resistant glass container;
step 2: the high pressure resistant glass container was filled with nitrogen gas and sealed in a vacuum state.
And step 3: and (3) placing the sealed container in an oven, heating to 180-200 ℃, and preserving heat for more than 12 hours.
And 4, step 4: and cooling the reactant to room temperature, filtering, washing and precipitating by using N-methyl pyrrolidone, ethanol and dichloromethane respectively, and drying for not less than 6 hours at the temperature of 40-60 ℃ in vacuum to obtain the ultrathin nanobelt of the phthalocyanine-based two-dimensional COF material, wherein the yield is about 80%.
Further, p-tert-butylaniline is a steric regulator and may be substituted with substituted aromatic monoamines.
Further, p-phenylenediamine, which is a linear linking group of COF materials, may be replaced with other linear aromatic diamines such as 4, 4' -biphenyldiamine.
Further, the central metal Cu in Cu (TAPc) may be replaced by other metal capable of forming a complex with phthalocyanine, such as Fe, Co, Ni, Zn, etc.
Further, the ultra-thin nanoribbons of phthalocyanine-based two-dimensional COF material obtained therein have a high degree of order, and have a length of about 20 μm at the longest, a width of about 50nm at the minimum, and a thickness of about 5nm at the thinnest.
Further, the length of the ultrathin nanobelt can be adjusted within the range of 5-20 μm, the width can be adjusted within the range of 50-200nm, and the thickness can be adjusted within the range of 5-10nm by adjusting the addition amount of the p-tert-butylaniline.
The invention introduces four anhydride groups into eight beta-positions of phthalocyanine to obtain dehydrated anhydride Cu (TAPc) of 2,3,9,10,16,17,23, 24-octacarboxyl copper phthalocyanine. A series of ultra-thin nanobelt materials of phthalocyanine-based two-dimensional organic framework materials are obtained by taking Cu (TAPc), p-phenylenediamine, biphenyldiamine and other linear aromatic diamines as basic building units, taking isoquinoline (0.05mL) as a catalyst and adding a large amount of p-tert-butyl aniline as a steric hindrance regulator in a mixed solvent (volume ratio is 1:1) of nitrogen methyl pyrrolidone and n-butyl alcohol. The length of the ultrathin nanobelt of the phthalocyanine-based two-dimensional organic framework material prepared by the synthesis method is about 20 microns at the longest, the width is about 50nm at the smallest, the thickness is about 5nm at the thinnest, and the synthesized ultrathin nanobelt has high orderliness. Particularly, by utilizing the synthesis method, the length, the width and the thickness of the ultrathin nanobelt can be adjusted by adjusting the addition of the p-tert-butyl aniline, wherein the length adjustment range is 5-20 mu m, the width adjustment range is 50-200nm, and the thickness adjustment range is 5-10 nm. In the method, the p-tert-butyl aniline plays a role of a steric hindrance regulator, and the growth of the phthalocyanine-based two-dimensional organic framework material towards one dominant direction can be controlled, so that the ultra-thin nano-belt-shaped appearance is formed. The aromatic monoamines with substituents and similar to the p-tert-butyl aniline structure can play a similar steric hindrance effect, and other linear aromatic diamines can be used for constructing frames with different topological structures instead of biphenyldiamine, so that the preparation method provided by the invention can be used for synthesizing various ultra-thin nanobelt materials of phthalocyanine-based two-dimensional COF materials with different functional properties.
The synthesis method of the phthalocyanine-based two-dimensional organic framework material ultrathin nanobelt provided by the invention can realize the controlled growth of the phthalocyanine-based two-dimensional COF material by only adding a large amount of steric hindrance regulators in the process of synthesizing the COF material by utilizing Cu (TAPc) and p-phenylenediamine, thereby obtaining the ultrathin nanobelt-shaped nano material. The required equipment is simple, the operation is cheap, and the industrial production is easy to realize. The universality is good, similar steric hindrance effect can be achieved by utilizing aromatic monoamines with substituents which are similar to the p-tert-butyl aniline structure, and other linear aromatic diamines can be used for constructing frames with different topological structures instead of biphenyldiamine.
The invention has the beneficial effects that: the phthalocyanine-based two-dimensional COF nano material with the ultrathin nano-band structure is obtained by adding a steric hindrance regulator in the synthesis process of the phthalocyanine-based two-dimensional COF material for utilization and controlling the growth direction of the COF material. The preparation method has the advantages of simple process, easily controlled synthesis conditions, high product yield, easy purification and separation, and easy realization of industrial production. In addition, the synthesis method has good universality and can be used for synthesizing a plurality of ultrathin nanobelt materials of phthalocyanine-based two-dimensional COF materials with different functional properties.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic view of the molecular structures of Cu (TAPc) (a), p-phenylenediamine (b) and p-tert-butylaniline (c).
FIG. 2 is a powder X-ray diffraction pattern of ultrathin nanoribbons of the prepared phthalocyanine-based two-dimensional COF material;
fig. 3 is an infrared spectrum of ultra-thin nanoribbons of a phthalocyanine-based two-dimensional COF material prepared;
fig. 4 is an ultraviolet-visible absorption spectrum of an ultrathin nanobelt of the prepared phthalocyanine-based two-dimensional COF material;
FIG. 5 is a TEM image of ultrathin nanobelts of the prepared phthalocyanine-based two-dimensional COF material, which is about 20 μm in length and about 50nm in width;
fig. 6 is an AFM image of ultra-thin nanoribbons of phthalocyanine-based two-dimensional COF material prepared, from which it can be seen that the thickness is about 5 nm.
Detailed Description
Examples 1,
Dissolving 17mg of Cu (TAPc), 4.3mg of p-phenylenediamine and 128. mu.L of p-tert-butylaniline in 1ml of a mixed solvent of N-methylpyrrolidone and n-butanol, and transferring the solution into a glass tube with a diameter of 0.5 cm; filling nitrogen into the glass tube, and sintering and sealing the glass tube by using an alcohol blast burner; placing the sealed glass tube in an oven, heating to 185 ℃, and preserving heat for 12 h; and cooling the reactant to room temperature, filtering, washing and precipitating by using N-methyl pyrrolidone, ethanol and dichloromethane respectively, and drying for 8 hours at the temperature of 40 ℃ in vacuum to obtain the ultra-thin nanobelt of the phthalocyanine-based two-dimensional COF material, wherein the yield is 78%.
Examples 2,
Dissolving 34mg of Cu (TAPc), 8.6mg of p-phenylenediamine and 256. mu.L of p-tert-butylaniline in 1ml of a mixed solvent of N-methylpyrrolidone and n-butanol, and transferring the solution into a glass tube with a diameter of 0.5 cm; filling nitrogen into the glass tube, and sintering and sealing the glass tube by using an alcohol blast burner; placing the sealed glass tube in an oven, heating to 180 ℃, and preserving heat for 20 hours; and cooling the reactant to room temperature, filtering, washing and precipitating by using N-methyl pyrrolidone, ethanol and dichloromethane respectively, and drying for 6 hours at the temperature of 40 ℃ in vacuum to obtain the ultra-thin nanobelt of the phthalocyanine-based two-dimensional COF material, wherein the yield is 80%.
Example 3, 43mg of Cu (TAPc), 11mg of p-phenylenediamine and 330. mu.L of p-tert-butylaniline were dissolved in 2ml of a mixed solvent of N-methylpyrrolidone and n-butanol, and then transferred into a glass tube having a diameter of 0.5 cm; filling nitrogen into the glass tube, and sintering and sealing the glass tube by using an alcohol blast burner; placing the sealed glass tube in an oven, heating to 200 ℃, and preserving heat for 12 h; and cooling the reactant to room temperature, filtering, washing and precipitating by using N-methyl pyrrolidone, ethanol and dichloromethane respectively, and drying for 6 hours at the temperature of 40 ℃ in vacuum to obtain the ultra-thin nanobelt of the phthalocyanine-based two-dimensional COF material, wherein the yield is 80%.
The above description is only given by way of example of the ultra-thin nanobelt of phthalocyanine-based two-dimensional COF material constructed by Cu (TAPc), p-phenylenediamine and p-tert-butylaniline, and is a preferred embodiment of the present invention, but the present invention is not limited thereto in any way; the present invention can be smoothly implemented by those skilled in the art in the light of the accompanying drawings and the above description; however, those skilled in the art should, upon attaining an understanding of the present disclosure, appreciate that many changes, modifications, and equivalents may be made to the invention without departing from the spirit and scope of the invention; meanwhile, any changes, modifications, evolutions, etc. of the equivalent changes made to the above embodiments according to the implementation technology of the present invention are within the protection scope of the technical solution of the present invention.
Claims (4)
1. A preparation method of an ultrathin nanobelt made of a phthalocyanine-based two-dimensional organic framework material is characterized by comprising the following specific steps:
step 1: dissolving Cu (TAPc), p-phenylenediamine and p-tert-butylamine in a mixed solvent of N-methyl pyrrolidone and n-butyl alcohol according to the molar weight ratio of 1:2-2.1:40-45, wherein the sum of the total mass of three ligands added in each milliliter of the mixed solvent is 20-50 mg, and then transferring the mixed solvent into a high-pressure resistant glass container;
step 2: filling nitrogen into the high-pressure-resistant glass container, and vacuumizing and sealing the high-pressure-resistant glass container;
and step 3: placing the sealed container in an oven, heating to 180-200 ℃, and preserving heat for more than 12 hours;
and 4, step 4: cooling the reactant to room temperature, filtering, washing and precipitating by using N-methyl pyrrolidone, ethanol and dichloromethane respectively, and drying for not less than 6 hours at the temperature of 40-60 ℃ in vacuum to obtain the ultra-thin nanobelt of the phthalocyanine-based two-dimensional COF material, wherein the yield reaches 80%;
the obtained ultrathin nanobelt of the phthalocyanine-based two-dimensional COF material has high orderliness, the length is 20 microns at the longest, the width is 50nm at the minimum, and the thickness is 5nm at the thinnest;
wherein the molecular structure of Cu (TAPc) is
2. The method for preparing ultra-thin nanoribbons of phthalocyanine-based two-dimensional organic framework material as claimed in claim 1, wherein p-phenylenediamine is a linear linking group of COF material, and is substituted with 4, 4' -biphenyldiamine.
3. The method for preparing ultra-thin nanoribbons of phthalocyanine-based two-dimensional organic framework material as claimed in claim 1, wherein the central metal Cu in Cu (TAPc) is replaced by other metal forming complexes with phthalocyanine, said metal comprising Fe, Co, Ni, Zn.
4. The method for preparing the ultra-thin nanobelt of phthalocyanine-based two-dimensional organic framework material according to claim 1, wherein the length of the ultra-thin nanobelt is adjusted within the range of 5 to 20 μm, the width is adjusted within the range of 50 to 200nm, and the thickness is adjusted within the range of 5 to 10nm by adjusting the amount of p-tert-butylaniline added.
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