CN114573826B - Two-dimensional metal organic framework based on isocyano coordination, preparation method and application - Google Patents

Two-dimensional metal organic framework based on isocyano coordination, preparation method and application Download PDF

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CN114573826B
CN114573826B CN202210185948.3A CN202210185948A CN114573826B CN 114573826 B CN114573826 B CN 114573826B CN 202210185948 A CN202210185948 A CN 202210185948A CN 114573826 B CN114573826 B CN 114573826B
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苏跃增
庄小东
何奇川
黄森鹤
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Abstract

The invention discloses a two-dimensional metal organic framework, a preparation method and application. The two-dimensional metal organic framework is formed by coordination of isocyano porphyrin and metal, wherein C in isocyano group on the isocyano porphyrin is connected with the metal through a coordination bond. The invention fills the blank that no metal-carbon coordinated metal organic framework exists so far, and provides possibility for researching the application of the material in the fields of sensing, energy storage, conversion and the like.

Description

Two-dimensional metal organic framework based on isocyano coordination, preparation method and application
Technical Field
The invention relates to the field of two-dimensional metal organic frameworks, in particular to a two-dimensional metal organic framework based on isocyano coordination, a preparation method and application.
Background
Metal-organic frameworks, a typical inorganic-organic hybrid, can be formed by coordination of a large number of organic ligands to metal nodes. The metal organic framework material has wide application prospect in the fields of gas separation, storage and the like by virtue of high porosity and high specific surface area. However, most conventional metal organic framework materials suffer from wide band gap, low conductivity and low carrier mobility, which greatly limits their applications in energy conversion and multifunctional electronic devices such as electrochemical sensing, electrocatalysis, photocatalysis, optoelectronics, spintronics, batteries and supercapacitors. Therefore, how to design and prepare a metal organic framework material with high conductivity so as to apply the metal organic framework material to advanced electronic device devices is a key point in the research field of metal organic framework materials.
With the continuous research on the intrinsic conductive properties of the metal organic framework materials and the continuous development of conductive property tests (such as conductivity tests and carrier mobility tests), a series of metal organic framework materials with high conductivity emerge, wherein two-dimensional metal organic framework materials stand out. The two-dimensional metal organic framework material has a unique layered structure, weak van der waals acting force exists between layers, and a two-dimensional plane of the two-dimensional metal organic framework material consists of organic building blocks and metal coordination connection units. Meanwhile, the carriers are highly delocalized in the plane of the two-dimensional metal organic framework, so that the organic-inorganic composite material has the advantages of high conductivity and high mobility. Besides the properties of adjustable porosity, high specific surface area, definite active sites and the like of the traditional metal organic framework, the two-dimensional metal organic framework material also shows unique chemical and physical properties, such as high conductivity, high stability, electrochemical activity, band gap adjustability, ferromagnetic ordering, optical activity and the like. The unique property of the two-dimensional metal organic framework material enables the two-dimensional metal organic framework material to have wide application prospect in a photoelectric electromagnetic device. In the reported conductive two-dimensional metal organic framework materials, the organic ligands mainly comprise nitrogen-containing organic ligands, oxygen-containing organic ligands and sulfur-containing organic ligands, which respectively correspond to the coordination modes of metal-nitrogen coordination, metal-oxygen coordination and metal-sulfur coordination. Around the organic ligands and coordination modes described above, a large number of two-dimensional metal-organic framework materials with high conductivity and excellent electrochemical sensing properties have been reported. However, the coordination elements in the organic ligands in the field are still limited to nitrogen, oxygen and sulfur elements, which limits the further development and application of such framework materials.
Therefore, those skilled in the art have been devoted to developing a two-dimensional metal-organic framework containing a new coordination mode to obtain higher conductivity and electrochemical sensing performance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a two-dimensional metal-organic framework containing a novel coordination system.
In order to achieve the above object, the present invention provides a two-dimensional metal-organic framework, the two-dimensional metal-organic framework is formed by coordination of isocyano porphyrin and metal M, wherein C in isocyano group on the isocyano porphyrin is connected with metal M through coordination bond, and the two-dimensional metal-organic framework has a structure as shown in the following:
Figure BDA0003523418390000021
wherein R is alkyl, aryl or alkoxy;
n is 0,1,2,3 or 4.
Preferably, the metal M is Mn, fe, co, rh, pd, ag, re or Pt.
Preferably, R is C 1 -C 4 Alkyl, phenyl or C 1 -C 4 An alkoxy group.
Preferably, R is methyl.
Preferably, n =2.
Preferably, the isocyanoporphyrin ligand has the structure:
Figure BDA0003523418390000031
preferably, M is Co.
The invention also provides a preparation method of the two-dimensional metal-organic framework, the two-dimensional metal-organic framework is formed by coordination of an isocyano porphyrin ligand and a metal M, wherein C in isocyano group on the isocyano porphyrin is connected with the metal M through a coordination bond, and the preparation method comprises the following steps:
adding the isocyano porphyrin ligand and metal M salt into absolute ethyl alcohol, stirring to obtain a precipitate, separating the precipitate, washing and drying to obtain the two-dimensional metal organic framework;
wherein the structure of the isocyano porphyrin ligand is shown as follows:
Figure BDA0003523418390000032
the two-dimensional metal-organic framework has the following structure:
Figure BDA0003523418390000041
wherein R is alkyl, aryl or alkoxy;
n is 0,1,2,3 or 4.
Preferably, the metal M is Mn, fe, co, rh, pd, ag, re or Pt.
Further, the preparation method of the isocyano porphyrin ligand comprises the following steps:
step S1, dissolving bromobenzene substituted by R group in anhydrous tetrahydrofuran, cooling to-78 ℃, adding N-butyllithium N-hexane solution, stirring at-78 ℃, then adding anhydrous N, N-dimethylformamide, continuing stirring, heating to room temperature after the reaction is finished, washing, separating, drying and purifying to obtain a product 1, wherein the structural formula of the product is shown as the following formula (1):
Figure BDA0003523418390000042
s2, dissolving pyrrole and the product 1 in absolute ethyl alcohol in a nitrogen atmosphere, then adding a hydrochloric acid solution into a reaction mixture and continuously stirring, after the reaction is finished, adding chloroform into the reaction mixture, washing and drying the obtained organic phase, adding tetrachloro-p-benzoquinone, keeping a reflux state for at least 1 hour, removing the reaction solvent, washing and purifying to obtain a product 2, wherein the structural formula of the product is shown as the following formula (2):
Figure BDA0003523418390000051
s3, dropwise adding fuming nitric acid into the chloroform solution of the product 2 at 0 ℃ in a nitrogen atmosphere, continuously stirring, quenching the reaction after the reaction is finished, removing the reaction solvent, washing and purifying to obtain a product 3, wherein the structural formula of the product is shown as the following formula (3):
Figure BDA0003523418390000052
step S4, adding a concentrated hydrochloric acid solution of stannous chloride dihydrate and the product 3 into the concentrated hydrochloric acid, continuously stirring at 60-80 ℃, neutralizing the reaction solution until the pH value is 7 after the reaction is finished, filtering, washing, drying and purifying to obtain a product 4, wherein the structural formula of the product is shown as the following formula (4):
Figure BDA0003523418390000053
and S5, dissolving the product 4 and benzyltriethylammonium chloride in dichloromethane in a nitrogen atmosphere, then adding a potassium hydroxide solution, adding chloroform into the two-phase mixture, heating for reflux reaction, and after the reaction is finished, washing, drying, concentrating and purifying to obtain the isocyano porphyrin ligand.
The invention also provides an application of the two-dimensional metal organic framework or the two-dimensional metal organic framework prepared by the method in electrochemical nitrogen dioxide sensing.
The invention has at least the following technical effects:
the invention synthesizes a two-dimensional metal organic framework by the coordination reaction of the isocyano porphyrin ligand and metal, fills the blank that no metal-carbon coordination metal organic framework exists so far, and provides possibility for researching the application of the material in the fields of sensing, photoelectricity, catalysis and the like.
And the metal organic framework material shows high selectivity and quick response performance to nitrogen dioxide gas under the room temperature condition, for example, the response time of the material is about 300 seconds under the nitrogen dioxide concentration of 10 ppm.
The conception, specific structure and technical effects of the present invention will be further described in conjunction with the accompanying drawings to fully understand the purpose, characteristics and effects of the present invention.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a ligand of isocyano porphyrin in accordance with a preferred embodiment of the present invention;
FIG. 2 is a schematic diagram of a two-dimensional metal organic framework compound synthesis according to a preferred embodiment of the present invention;
FIG. 3 is a NMR spectrum of 5,10,15,20-tetrakis (2,6-dimethylphenyl) porphyrin prepared in accordance with a preferred embodiment of the present invention;
fig. 4 is an electrochemical nitrogen dioxide sensing response curve of a two-dimensional metal organic framework according to a preferred embodiment of the present invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Definition and clarification of terms
Before describing the details of the embodiments, some terms are defined or clarified.
Unless specifically defined otherwise, R and any other variables are generic nomenclature. The specific definitions of the formulae given herein govern the formula.
The term "alkyl" is intended to mean a group derived from an aliphatic hydrocarbon and includes straight chain, branched or cyclic alkyl groups. A group "derived from" a compound indicates a group formed by the removal of one or more H or D. In some embodiments, the alkyl group has 1-20 carbon atoms.
The term "C 1 -C 4 Alkyl "is intended to mean an alkyl group having 1 to 4 carbon atoms.
The term "alkoxy" is intended to denote the group RO-, wherein R is alkyl.
The term "C 1 -C 4 Alkoxy "refers to an alkoxy group having 1 to 4 carbon atoms.
The term "aryl" is intended to mean a group derived from an aromatic hydrocarbon having one or more points of attachment. The term includes groups having a single ring and groups having multiple rings that may be connected by single bonds or fused together.
All groups may be substituted or unsubstituted. The substituents are discussed below. In structures where the substituted bond traverses one or more rings, as shown below,
Figure BDA0003523418390000071
this means that the substituent R may be bonded at any available position on one or more rings.
The term "metal M" is intended to mean that M is a metal element, for example, the metal M may be Pt, ir, rh, pd, ni, au, ag, cr, co, mo, mn, re, or Fe, and the like.
The term "metal M salt" is intended to mean a salt comprising a metal M, for example the metal M salt may be FeCl 3 ，CoCl 2 ，MnSO 4 ，PtCl 2 Or Cr (NO) 3 ) 3 And so on.
Example 1
1) Isocyanoporphyrin ligand R- i Preparation of CN-Por:
step 1, in a dry Shi Laike tube (Schlenk) equipped with a magnetic stirrer, bromobenzene substituted by an R group is dissolved in anhydrous tetrahydrofuran and cooled to-78 ℃, then N-butyllithium hexane solution is dropwise added, stirring is carried out at-78 ℃ for 30 minutes, then anhydrous N, N-dimethylformamide is added, stirring is carried out for 1 hour, and the temperature is raised to the room temperature. After the raw material is completely consumed, saturated NH is used 4 The reaction was quenched with aqueous Cl, the solvent was removed and the residue was extracted with ethyl acetate and the extract was extracted with saturated NaHCO 3 The aqueous solution was washed and MgSO 4 Drying, removing the solvent under reduced pressure, and subjecting to flash column chromatography to obtain product 1 having a structural formula shown in formula (1) below:
Figure BDA0003523418390000072
wherein, the R group can be alkyl, aryl or alkoxy; n is 0,1,2,3 or 4.
Step 2, dissolving pyrrole and product 1 in absolute ethanol under nitrogen atmosphere and continuously stirring for 10 minutes. The hydrochloric acid solution was then added to the reaction mixture and stirring was continued for 16 hours. After completion of the reaction, chloroform was added to the reaction mixture, and the resulting organic phase was washed with a saturated aqueous sodium hydrogencarbonate solution and dried over anhydrous magnesium sulfate. Tetrachlorop-benzoquinone was then added to the solution and maintained at reflux for 1 hour. After the reaction was cooled to room temperature, the reaction solvent was removed by rotary evaporation and washed with methanol and petroleum ether. The crude product was purified by silica gel column chromatography eluting with n-hexane/dichloromethane to give product 2, which has the formula (2) below:
Figure BDA0003523418390000081
wherein, the R group can be alkyl, aryl or alkoxy; n is 0,1,2,3 or 4.
And 3, dropwise adding fuming nitric acid into the chloroform solution of the product 2 at 0 ℃ under a nitrogen atmosphere, and stirring for 30 minutes. After the reaction was completed, an aqueous ammonia solution was added to the reaction mixture to quench it, and the solvent in the organic phase was removed by rotary evaporation. The brown powder obtained was washed with deionized water and the crude product obtained was purified by silica gel column chromatography using a petroleum ether/ethyl acetate solution as eluent to give product 3, which has the formula (3) shown below:
Figure BDA0003523418390000082
wherein, the R group can be alkyl, aryl or alkoxy; n is 0,1,2,3 or 4.
Step 4, adding the concentrated hydrochloric acid solution of stannous chloride dihydrate and the product 3 into concentrated hydrochloric acid, and continuously stirring at 70 ℃ for 7 hours. After the reaction is finished, the reaction system is cooled by using a cold water bath and an ice water bath, and then the reaction mixture is neutralized by using sodium hydroxide until the pH value of the solution is about 7.0. The crude solid was obtained after filtration, washing with deionized water and vacuum drying. The crude product was further purified by Soxhlet extraction to give product 4, which has the formula (4) below:
Figure BDA0003523418390000091
wherein, the R group can be alkyl, aryl or alkoxy; n is 0,1,2,3 or 4.
And 5, dissolving the product 4 and benzyltriethylammonium chloride in dichloromethane in a nitrogen atmosphere, and then adding a 45% by mass potassium hydroxide solution. Adding chloroform to the biphasic mixtureAnd refluxed overnight. After the reaction was completed and the temperature was decreased to room temperature, the mixture was transferred to a separatory funnel and washed twice and once with deionized water and saturated brine, respectively. The organic phase was collected and dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to give a crude product. The crude product was purified by silica gel column chromatography eluting with petroleum ether/ethyl acetate to give the product 5, isocyano porphyrin ligand R- i CN-Por, the structural formula of which is shown as the following formula:
Figure BDA0003523418390000092
wherein, the R group can be alkyl, aryl or alkoxy; n is 0,1,2,3 or 4..
2) Based on the isocyano porphyrin ligand R- i Preparation of CN-Por coordinated two-dimensional metal organic framework:
r- i CN-Por and metal M salt were added to absolute ethanol and the formation of a flocculent solid was observed. Stir vigorously at room temperature for 12 hours. After the reaction is finished, rapidly centrifuging in absolute ethyl alcohol to remove unreacted metal M salt and organic ligand, and obtaining a two-dimensional metal organic framework M-R- i CN-Por, the preparation method is shown below.
Figure BDA0003523418390000101
Wherein, the R group can be alkyl, aryl or alkoxy; n is 0,1,2,3 or 4.
Two-dimensional metal organic framework M-R- i The metal M in CN-Por can be Mn, fe, co, rh, pd, ag, re, pt, etc.
Example 2
A method for synthesizing a two-dimensional metal organic framework based on coordination of isocyano porphyrin and cobalt, wherein a diagram 1 shows isocyano porphyrin ligand i The preparation process of CN-Por, FIG. 2 shows two-dimensional metal organic framework Co- i CN-Por preparation process. Isocyanoporphyrin ligands i Of CN-PorThe structure is shown as formula (A):
Figure BDA0003523418390000102
two-dimensional metal organic framework Co- i The structure of CN-Por is shown as formula (B):
Figure BDA0003523418390000111
the preparation method comprises the following specific steps:
1) Isocyanoporphyrin ligands i Preparation of CN-Por:
step 1, dissolving 2,6-dimethylbromobenzene in anhydrous tetrahydrofuran in a drying Shi Laike tube (Schlenk) provided with a magnetic stirrer, cooling to-78 ℃, then dropwise adding N-butyllithium N-hexane solution, stirring at-78 ℃ for 30 minutes, then adding anhydrous N, N-dimethylformamide, stirring for 1 hour, and heating to room temperature. After the raw material is completely consumed, saturated NH is used 4 The reaction was quenched with aqueous Cl, the solvent was removed and the residue was extracted with ethyl acetate and the extract was extracted with saturated NaHCO 3 The aqueous solution was washed and MgSO 4 Drying, removal of the solvent under reduced pressure and flash column chromatography afforded the product 2,6-Dimethylbenzaldehyde (2,6-dimethyllbenzaldehyde).
Step 2, dissolving pyrrole and 2,6-dimethylbenzaldehyde in absolute ethanol under nitrogen atmosphere and continuously stirring for 10 minutes. The hydrochloric acid solution was then added to the reaction mixture and stirring was continued for 16 hours. After completion of the reaction, chloroform was added to the reaction mixture, and the resulting organic phase was washed with a saturated aqueous sodium hydrogencarbonate solution and dried over anhydrous magnesium sulfate. Tetrachlorop-benzoquinone was then added to the solution and maintained at reflux for 1 hour. After the reaction was cooled to room temperature, the reaction solvent was removed by rotary evaporation and washed with methanol and petroleum ether. The resulting crude product was purified by silica gel column chromatography eluting with n-hexane/dichloromethane to give the product 5,10,15,20-tetrakis (2,6-dimethylphenyl) porphyrin (5,10,15,20-tetrakis (2,6-dimethylphenyl) porphyrins). 5,10,15,20The NMR spectrum of-tetrakis (2,6-dimethylphenyl) porphyrin is shown in FIG. 3: 1H NMR (500MHz, CDCl) 3 ,δ):8.62(s,8H,phenylβ–pyrrolic-H),7.59(m,4H,phenyl p-H),7.47(d,8H,phenyl m-H),1.90(24H,phenyl o-CH 3 )and-2.47(brs,2H,internal NH).
And 3, dropwise adding fuming nitric acid into a chloroform solution of 5,10,15,20-tetrakis (2,6-dimethylphenyl) porphyrin at 0 ℃ under a nitrogen atmosphere, and stirring for 30 minutes. After the reaction was completed, an aqueous ammonia solution was added to the reaction mixture to quench it, and the solvent in the organic phase was removed by rotary evaporation. The resulting brown powder was washed with deionized water and the resulting crude product was purified by silica gel column chromatography eluting with petroleum ether/ethyl acetate solution to give the product 5,10,15,20-tetrakis (2,6-dimethyl-4-nitrophenyl) porphyrin (5,10,15,20-tetrakis (2,6-dimethyl-4-nitrophenyl) porphyrins).
Step 4, adding concentrated hydrochloric acid solution of stannous chloride dihydrate and 5,10,15,20-tetrakis (2,6-dimethyl-4-nitrophenyl) porphyrin to concentrated hydrochloric acid, and continuously stirring at 70 ℃ for 7 hours. After the reaction is finished, the reaction system is cooled by using a cold water bath and an ice water bath, and then the reaction mixture is neutralized by using sodium hydroxide until the pH value of the solution is about 7.0. The crude product solid was obtained after filtration, washing with deionized water and vacuum drying. The crude product was further purified by Soxhlet extraction to give 5,10,15,20-tetrakis (2,6-dimethyl-4-aminophenyl) porphyrin (5,10,15,20-tetrakis (2,6-dimethyl-4-aminophenyl) porphins).
Step 5, dissolving 5,10,15,20-tetrakis (2,6-dimethyl-4-aminophenyl) porphyrin and benzyltriethylammonium chloride in dichloromethane under nitrogen atmosphere, and then adding 45% by mass potassium hydroxide solution. Chloroform was added to the biphasic mixture and refluxed overnight. After the reaction was completed and the temperature was decreased to room temperature, the mixture was transferred to a separatory funnel, and washed twice and once with deionized water and saturated brine, respectively. The organic phase was collected and dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to give a crude product. The crude product was purified by silica gel column chromatography eluting with petroleum ether/ethyl acetate to give the isocyanoporphyrin ligand i CN-Por。
2) Two-dimensional metal organic framework Co- i Preparation of CN-Por:
the ligand of isocyano porphyrin i CN-Por and CoCl 2 ·6H 2 When O was added to absolute ethanol, generation of a flocculent solid was observed. Stir vigorously at room temperature for 12 hours. After the reaction is finished, rapidly centrifuging in absolute ethyl alcohol to remove unreacted CoCl 2 ·6H 2 O and organic ligand, vacuum drying to obtain two-dimensional metal organic framework Co- i CN-Por。
3) Two-dimensional metal organic framework Co- i Electrochemical nitrogen dioxide sensing response of CN-Por:
FIG. 4 is a two-dimensional metal organic framework Co- i CN-Por electrochemical nitrogen dioxide sensing response curve. As shown in fig. 4, a two-dimensional metal-organic framework Co- i CN-Por showed high selectivity to nitrogen dioxide and fast response at room temperature, with the response time of the material being about 300 seconds at a nitrogen dioxide concentration of 10 ppm.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.

Claims (8)

1. A two-dimensional metal-organic framework, wherein the two-dimensional metal-organic framework is formed by coordination of isocyano porphyrin and metal M, wherein C in isocyano group on the isocyano porphyrin is connected with the metal M through a coordination bond, and the two-dimensional metal-organic framework has a structure as shown in the following:
Figure FDA0003848825320000011
wherein R is alkyl, aryl or alkoxy;
n is 0,1,2,3 or 4;
the metal M is Mn, fe, co, rh, pd, ag, re or Pt.
2. The two-dimensional metal-organic framework of claim 1, wherein R is C 1 -C 4 Alkyl, phenyl or C 1 -C 4 An alkoxy group.
3. The two-dimensional metal-organic framework of claim 1, wherein R is methyl.
4. A two-dimensional metal-organic framework according to claim 3, wherein n =2.
5. The two-dimensional metal-organic framework of claim 1, wherein the isocyanoporphyrin ligand has the structure:
Figure FDA0003848825320000021
6. a preparation method of a two-dimensional metal-organic framework is characterized in that the two-dimensional metal-organic framework is formed by coordination of an isocyano porphyrin ligand and a metal M, wherein C in isocyano group on the isocyano porphyrin is connected with the metal M through a coordination bond, and the preparation method comprises the following steps:
adding the isocyano porphyrin ligand and metal M salt into absolute ethyl alcohol, stirring to obtain a precipitate, separating the precipitate, washing and drying to obtain the two-dimensional metal organic framework;
wherein the structure of the isocyano porphyrin ligand is shown as follows:
Figure FDA0003848825320000022
the two-dimensional metal-organic framework has the following structure:
Figure FDA0003848825320000031
wherein R is alkyl, aryl or alkoxy;
n is 0,1,2,3 or 4;
the metal M is Mn, fe, co, rh, pd, ag, re or Pt.
7. The method of claim 6, wherein the step of preparing the isocyanoporphyrin ligand comprises:
step S1, dissolving bromobenzene substituted by R group in anhydrous tetrahydrofuran, cooling to-78 ℃, adding N-butyllithium N-hexane solution, stirring at-78 ℃, then adding anhydrous N, N-dimethylformamide, continuing stirring, heating to room temperature after the reaction is finished, washing, separating, drying and purifying to obtain a product 1, wherein the structural formula of the product is shown as the following formula (1):
Figure FDA0003848825320000032
s2, dissolving pyrrole and the product 1 in absolute ethyl alcohol in a nitrogen atmosphere, then adding a hydrochloric acid solution into a reaction mixture and continuously stirring, after the reaction is finished, adding chloroform into the reaction mixture, washing and drying the obtained organic phase, adding tetrachloro-p-benzoquinone, keeping a reflux state for at least 1 hour, removing the reaction solvent, washing and purifying to obtain a product 2, wherein the structural formula of the product is shown as the following formula (2):
Figure FDA0003848825320000041
s3, dropwise adding fuming nitric acid into the chloroform solution of the product 2 at 0 ℃ in a nitrogen atmosphere, continuously stirring, quenching the reaction after the reaction is finished, removing the reaction solvent, washing and purifying to obtain a product 3, wherein the structural formula of the product is shown as the following formula (3):
Figure FDA0003848825320000042
step S4, adding a concentrated hydrochloric acid solution of stannous chloride dihydrate and the product 3 into the concentrated hydrochloric acid, continuously stirring at 60-80 ℃, neutralizing the reaction solution until the pH value is 7 after the reaction is finished, filtering, washing, drying and purifying to obtain a product 4, wherein the structural formula of the product is shown as the following formula (4):
Figure FDA0003848825320000043
and S5, dissolving the product 4 and benzyltriethylammonium chloride in dichloromethane in a nitrogen atmosphere, then adding a potassium hydroxide solution, adding chloroform into the two-phase mixture, heating for reflux reaction, and after the reaction is finished, washing, drying, concentrating and purifying to obtain the isocyano porphyrin ligand.
8. Use of a two-dimensional metal-organic framework according to any of claims 1-5 or a two-dimensional metal-organic framework prepared by a method according to any of claims 6-7 in electrochemical nitrogen dioxide sensing.
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