CN116284063A - Nitrogen-containing carboxylic acid transition metal complex and preparation method and application thereof - Google Patents
Nitrogen-containing carboxylic acid transition metal complex and preparation method and application thereof Download PDFInfo
- Publication number
- CN116284063A CN116284063A CN202310103899.9A CN202310103899A CN116284063A CN 116284063 A CN116284063 A CN 116284063A CN 202310103899 A CN202310103899 A CN 202310103899A CN 116284063 A CN116284063 A CN 116284063A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- carboxylic acid
- metal complex
- nitrogen
- containing carboxylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 50
- -1 Nitrogen-containing carboxylic acid transition metal Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000010668 complexation reaction Methods 0.000 title description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 33
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 28
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 10
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 8
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention provides a nitrogenous carboxylic acid transition metal complex, a preparation method and application thereof, and the chemical formula is [ Zn ] 3 (H 3 Ntba) 2 (4,4′‑bipy)] n Wherein H is 3 Ntba=4, 4',4 "-triphenylamine tricarboxylic acid, 4' -bipy=4, 4' -bipyridine. The preparation method is that 4,4 '-tricarboxylic acid triphenylamine is used as ligand, 4' -bipyridine is used as auxiliary ligand, and the mixture of N, N-dimethylformamide and N, N-dimethylacetamide is reacted with zinc nitrate to obtain the nitrogenous carboxylic acid transition metal complex. The complex belongs to an orthorhombic crystal system and a Cmca space group, and the unit cell parameters are as follows:
α=90°, β=90°, γ=90°. The preparation method is simple to operate and can be popularized and applied on a large scale. The invention also provides the application of the transition metal complex of the carboxylic acid containing nitrogen, which can be used as good CO 2 The gas adsorbs the separation material.
Description
Technical Field
The invention belongs to the technical field of preparation of metal organic complexes, and particularly relates to a nitrogenous carboxylic acid transition metal complex, and a preparation method and application thereof.
Background
With the development of scientific technology, the emission of carbon dioxide in the atmosphere is continuously increased due to the large-scale use of coal, petroleum, natural gas and the like, and a large amount of carbon dioxide is an intangible glass cover, so that long-wave radiation emitted by the ground surface can be absorbed and can not be subjected to heat exchange with an outer space, and the greenhouse effect is aggravated, thereby a series of environmental problems such as elevation of glacier melting sea level, abnormal climate, aggravation of land drought desertification and the like are brought. Therefore, the method for capturing and converting carbon dioxide quickly and efficiently is significant for solving the problems of environment and energy sources by aid of assistance.
The existing carbon dioxide capturing methods comprise absorption, membrane separation, adsorption and the like, and common materials for capturing carbon dioxide are as follows: activated carbon, calcium oxide-based adsorbents, nano-based adsorbents, potassium-based adsorbents, covalent organic materials, metal organic framework materials, and the like. The metal organic framework material has the structural characteristics of large specific surface area, high porosity, adjustable aperture, a large number of active sites and the like, is focused by researchers in recent years, and is applied to the fields of adsorption, sensing, catalysis and the like. The nitrogen-containing carboxylic acid transition metal complex takes metal ions as coordination centers to be connected to form 1D, 2D and 3D structures, and can be directly used as an adsorption material in the field of gas adsorption separation due to the unique porous structure characteristics of the nitrogen-containing carboxylic acid transition metal complex.
The invention uses the potential superior performance of triphenylamine 4,4' -tricarboxylic acid as a triangle nitrogenous tricarboxylic acid flexible ligand, and combines the flexible ligand with transition metal salt to prepare the transition metal complex with high porosity and large specific surface area. The complex has good pore structure characteristics and the difference of the adsorption capacity of the complex to different gas molecules, so that the separation effect of mixed gas is realized, and a good adsorption material is provided for the field of gas adsorption separation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a nitrogenous carboxylic acid transition metal complex, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme: a transition metal complex of nitrogenous carboxylic acid, a preparation method and application thereof are characterized in that the chemical formula of the transition metal complex of nitrogenous carboxylic acid is [ Zn ] 3 (H 3 Ntba) 2 (4,4′-bipy)] n Wherein H is 3 Ntba=4, 4',4 "-triphenylamine tricarboxylic acid, 4' -bipy=4, 4' -bipyridine;
the nitrogen-containing carboxylic acid transition metal complex belongs to an orthorhombic crystal system and a Cmca space group, and the unit cell parameters are as follows:
α＝90°，β＝90°，γ＝90°。
a preparation method of a nitrogen-containing carboxylic acid transition metal complex is characterized by comprising the following steps:
s1, sequentially adding zinc nitrate, 4 '-triphenylamine tricarboxylic acid and 4,4' -bipyridine into a glass bottle, then adding a mixed solvent of N, N-dimethylformamide and N, N-dimethylacetamide, and stirring for 30min at room temperature to obtain a mixed solution A;
s2, placing the mixed solution A obtained in the step S1 in a constant-temperature forced air drying oven, reacting for 48-72 h at the temperature of 90-100 ℃, taking out, naturally cooling to room temperature, sequentially washing with pure water and absolute ethyl alcohol for 3 times respectively, filtering, and drying to obtain yellow leaf-shaped crystals, namely the nitrogenous carboxylic acid transition metal complex.
The preparation method is to take zinc nitrate as transition metal salt, 4 '-triphenylamine tricarboxylic acid as ligand and 4,4' -bipyridine as auxiliary ligand.
Preferably, the molar ratio of zinc nitrate, triphenylamine 4,4 '-tricarboxylic acid, and 4,4' -bipyridine described in S1 is 5:2:3; the volume ratio of the N, N-dimethylformamide to the N, N-dimethylacetamide is 2:1; the dosage ratio of the zinc nitrate to the N, N-dimethylacetamide is 0.1mmol:1mL.
The nitrogen-containing carboxylic acid transition metal complex obtained by the invention uses an ASAP2020HD88 full-automatic micropore physical adsorption analyzer to analyze the specific surface area and the pore diameter of the material.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the nitrogenous carboxylic acid transition metal complex provided by the invention comprises the steps of sequentially mixing zinc nitrate, 4 '-tricarboxylic acid triphenylamine and 4,4' -bipyridine according to a certain proportion by a solvothermal method, adding a mixed solvent of N, N-dimethylformamide and N, N-dimethylacetamide, stirring, and reacting in an incubator for a certain time to obtain yellow leaf-shaped crystals, namely the nitrogenous carboxylic acid transition metal complex. The preparation method is simple to operate and can be popularized and applied on a large scale.
2. The nitrogenous carboxylic acid transition metal complex prepared by the invention takes zinc as a coordination center, 4 '-triphenylamine tricarboxylic acid is taken as a ligand, 4' -bipyridine is taken as an auxiliary ligand, and the obtained complex can be taken as good CO 2 The gas adsorbs the separation material.
The invention is described in further detail below with reference to the drawings and examples.
Drawings
FIG. 1 shows [ Zn ] prepared in example 1 of the present invention 3 (H 3 Ntba) 2 (4,4′-bipy)] n Is a diagram of an asymmetric structural unit of the above-mentioned structure.
FIG. 2 shows [ Zn ] prepared in example 1 of the present invention 3 (H 3 Ntba) 2 (4,4′-bipy)] n Is a three-dimensional structure of the (c).
FIG. 3 shows [ Zn ] prepared in example 1 of the present invention 3 (H 3 Ntba) 2 (4,4′-bipy)] n Comparison of the experimental adsorption isotherm (left: Y axis) with the simulated adsorption isotherm (left: Y axis) and equimolar binary mixture gas CO 2 /N 2 Adsorption selectivity separation ratio (right: Y axis).
Detailed Description
Example 1
This example provides a nitrogen-containing carboxylic acid transition metalComplex of the formula [ Zn ] 3 (H 3 Ntba) 2 (4,4′-bipy)] n Wherein H is 3 Ntba=4, 4',4 "-triphenylamine tricarboxylic acid, 4' -bipy=4, 4' -bipyridine. The preparation method of the complex comprises the following steps:
s1, sequentially adding 0.1mmol of zinc nitrate, 0.04mmol of 4,4 '-triphenylamine tricarboxylic acid and 0.06mmol of 4,4' -bipyridine into a 10mL glass bottle, adding 2mL of mixed solvent of N, N-dimethylformamide and 1mL of N, N-dimethylacetamide, and continuously stirring the mixture at room temperature for 30min to obtain a mixed solution A;
s2, placing the mixed solution A obtained in the S1 into a constant-temperature forced air drying oven, drying for 48 hours at the temperature of 95 ℃, taking out, naturally cooling to room temperature, washing with pure water and absolute ethyl alcohol for 3 times in sequence, filtering, and drying to obtain yellow leaf-shaped crystals which are nitrogenous carboxylic acid transition metal complexes [ Zn ] 3 (H 3 Ntba) 2 (4,4′-bipy)] n 。
The nitrogen-containing carboxylic acid transition metal complex prepared in the embodiment takes zinc as a coordination center, triphenylamine 4,4 '-tricarboxylic acid is taken as a ligand, 4' -bipyridine is taken as an auxiliary ligand, the complex is yellow leaf-shaped crystal, and the molecular formula is C 52 H 32 N 4 O 12 Zn 3 。
The basic structural unit diagram of the nitrogen-containing carboxylic acid transition metal complex prepared in the embodiment is shown in figure 1. Single crystal X-ray diffraction tests showed that: belongs to an orthorhombic crystal system, cmca space group, and the unit cell parameters are as follows:
α=90°, β=90°, γ=90°. The complex has a three-dimensional network structure, and each asymmetric structural unit contains three crystallographically independent zinc ions, two 4,4 '-tricarboxylic triphenylamine ligands and one 4,4' -bipyridine auxiliary ligand. The central metal ion Zn1 is 6 coordination structure and takes a regular octahedron configuration, wherein 6 oxygen atoms come from six 4,4' -tricarboxylic acid triphenylamine ligands, the metal ion Zn2 is 5 coordination structure and takes a deformed triangle bipyramid configuration, whereinThe 4 oxygen atoms are respectively from three 4,4 '-tricarboxylic acid triphenylamine ligands, and the 1 nitrogen atom is from a 4,4' -bipyridine auxiliary ligand. Part of the bond length of the transition metal complex of the carboxylic acid containing nitrogen>
Bond angles (°) are listed in table 1.
TABLE 1 partial bond lengths of nitrogen-containing carboxylic acid transition metal complexes
Bond angle (°)
The three-dimensional structure of the nitrogen-containing carboxylic acid transition metal complex prepared in the embodiment is shown in fig. 2, and the complex has obvious pore characteristics.
The nitrogen-containing carboxylic acid transition metal complex prepared in this example was analyzed by ASAP2020HD88 full-automatic microporous physical adsorption at 77K using N 2 The adsorption/desorption isotherm is measured for pore diameter and specific surface area, and the result shows that the specific surface area is 42.9m 2 And/g, average pore diameter of 3.5nm.
The nitrogen-containing carboxylic acid transition metal complex prepared in this example was used in a gas adsorption separation test at temperatures of 273K and 298K for CH 4 、CO 2 、N 2 、O 2 And (5) testing gas adsorption and desorption. The measurement results are as follows: at 273K, for N 2 The adsorption capacity of (C) is 0.84cm 3 /g, pair O 2 The adsorption capacity of (C) was 4.22cm 3 /g, for CO 2 The adsorption capacity of (C) is 24.05cm 3 /g, for CH 4 The adsorption capacity of (C) is 3.05cm 3 And/g. At 298K, for N 2 The adsorption capacity of (C) is 0.57cm 3 /g, pair O 2 The adsorption capacity of (C) is 1.45cm 3 /g, for CO 2 The adsorption capacity of (C) is 14.171cm 3 /g, for CH 4 The adsorption capacity of (C) was 2.94cm 3 And/g. It can be seen that the complex materials exhibit different adsorption capacities for different gases, whereinFor CO 2 The gas has good adsorption selectivity.
According to the single point Langmuir Freundlich model of Ideal Adsorption Solution Theory (IAST), the [ Zn ] activated at 273K and 298K were calculated from single component adsorption isotherms, respectively 3 (H 3 Ntba) 2 (4,4′-bipy)] n Equimolar binary mixture gas CO 2 /N 2 Is characterized by the adsorption separation selectivity of (1); wherein the adsorption selectivity S is defined as
As can be seen from FIG. 3, the nitrogen-containing carboxylic acid transition metal complex [ Zn ] prepared by this embodiment is at standard atmospheric pressure 3 (H 3 Ntba) 2 (4,4′-bipy)] n For CO 2 /N 2 The theoretical molar adsorption separation selectivity S of (2) is 750:1, which fully proves that the catalyst can be used as CO 2 The gas adsorbs the separated ideal material.
Example 2
The embodiment provides a preparation method of a nitrogen-containing carboxylic acid transition metal complex, which comprises the following steps:
s1, adding 0.2mmol of zinc nitrate, 0.08mmol of 4,4 '-triphenylamine tricarboxylic acid and 0.12mmol of 4,4' -bipyridine into a 25mL glass bottle in sequence, adding 4mL of mixed solvent of N, N-dimethylformamide and 2mL of N, N-dimethylacetamide, and continuously stirring the mixture at room temperature for 30min to obtain a mixed solution A;
s2, placing the mixed solution A obtained in the S1 into a constant-temperature forced air drying oven, drying for 48 hours at the temperature of 100 ℃, taking out, naturally cooling to room temperature, washing with pure water and absolute ethyl alcohol for 3 times in sequence, filtering, and drying to obtain yellow leaf-shaped crystals, namely the nitrogenous carboxylic acid transition metal complex [ Zn ] 3 (H 3 Ntba) 2 (4,4′-bipy)] n 。
The nitrogen-containing carboxylic acid transition metal complex prepared in the embodiment is yellow leaf-shaped crystal with specific surface area of 42.3m 2 And/g, average pore diameter of 3.6nm.
Example 3
The embodiment provides a preparation method of a nitrogen-containing carboxylic acid transition metal complex, which comprises the following steps:
s1, adding 0.2mmol of zinc nitrate, 0.08mmol of 4,4 '-triphenylamine tricarboxylic acid and 0.12mmol of 4,4' -bipyridine into a 25mL glass bottle in sequence, adding 4mL of mixed solvent of N, N-dimethylformamide and 2mL of N, N-dimethylacetamide, and continuously stirring the mixture at room temperature for 30min to obtain a mixed solution A;
s2, placing the mixed solution A obtained in the S1 into a constant-temperature forced air drying oven, drying for 60 hours at the temperature of 98 ℃, taking out, naturally cooling to room temperature, washing with pure water and absolute ethyl alcohol for 3 times in sequence, filtering, and drying to obtain yellow leaf-shaped crystals, namely the nitrogenous carboxylic acid transition metal complex [ Zn ] 3 (H 3 Ntba) 2 (4,4′-bipy)] n 。
The nitrogen-containing carboxylic acid transition metal complex prepared in the embodiment is yellow leaf-shaped crystal with specific surface area of 41.7m 2 And/g, average pore diameter of 4.2nm.
Example 4
The embodiment provides a preparation method of a nitrogen-containing carboxylic acid transition metal complex, which comprises the following steps:
s1, sequentially adding 0.1mmol of zinc nitrate, 0.04mmol of 4,4 '-triphenylamine tricarboxylic acid and 0.06mmol of 4,4' -bipyridine into a 10mL glass bottle, adding 2mL of mixed solvent of N, N-dimethylformamide and 1mL of N, N-dimethylacetamide, and continuously stirring the mixture at room temperature for 30min to obtain a mixed solution A;
s2, placing the mixed solution A obtained in the S1 into a constant-temperature forced air drying oven, drying for 56 hours at 93 ℃, taking out, naturally cooling to room temperature, washing with pure water and absolute ethyl alcohol for 3 times in sequence, filtering, and drying to obtain yellow leaf-shaped crystals, namely the nitrogenous carboxylic acid transition metal complex [ Zn ] 3 (H 3 Ntba) 2 (4,4′-bipy)] n 。
The nitrogen-containing carboxylic acid transition metal complex prepared in the embodiment is yellow leaf-shaped crystal with specific surface area of 41.9m 2 And/g, average pore diameter of 3.8nm.
Example 5
The embodiment provides a preparation method of a nitrogen-containing carboxylic acid transition metal complex, which comprises the following steps:
s1, sequentially adding 0.4mmol of zinc nitrate, 0.16mmol of 4,4 '-triphenylamine tricarboxylic acid and 0.24mmol of 4,4' -bipyridine into a 50mL glass bottle, adding 8mL of a mixed solvent of N, N-dimethylformamide and 4mL of N, N-dimethylacetamide, and continuously stirring the mixture at room temperature for 30min to obtain a mixed solution A;
s2, placing the mixed solution A obtained in the S1 into a constant-temperature forced air drying oven, drying for 72 hours at the temperature of 90 ℃, taking out, naturally cooling to room temperature, sequentially washing with pure water and absolute ethyl alcohol for 3 times respectively, filtering, and drying to obtain yellow leaf-shaped crystals, namely the nitrogenous carboxylic acid transition metal complex [ Zn ] 3 (H 3 Ntba) 2 (4,4′-bipy)] n 。
The nitrogen-containing carboxylic acid transition metal complex prepared in the embodiment is yellow leaf-shaped crystal with specific surface area of 41.6m 2 And/g, average pore diameter of 3.5nm.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (6)
1. A nitrogen-containing carboxylic acid transition metal porous complex is characterized in that the chemical formula of the nitrogen-containing carboxylic acid transition metal complex is [ Zn ] 3 (H 3 Ntba) 2 (4,4′-bipy)] n Wherein H is 3 Ntba=4, 4',4 "-triphenylamine tricarboxylic acid, 4' -bipy=4, 4' -bipyridine;
the nitrogen-containing carboxylic acid transition metal complex belongs to an orthorhombic crystal system and a Cmca space group, and the unit cell parameters are as follows:
α＝90°，β＝90°，γ＝90°。
2. a process for preparing the nitrogen-containing carboxylic acid transition metal complex as claimed in claim 1, which comprises:
s1, sequentially adding zinc nitrate, 4 '-triphenylamine tricarboxylic acid and 4,4' -bipyridine into a glass bottle, then adding a mixed solvent of N, N-dimethylformamide and N, N-dimethylacetamide, and stirring for 30min at room temperature to obtain a mixed solution A;
s2, placing the mixed solution A obtained in the step S1 in a constant-temperature forced air drying oven, reacting for 48-72 h at the temperature of 90-100 ℃, taking out, naturally cooling to room temperature, sequentially washing with pure water and absolute ethyl alcohol for 3 times respectively, filtering, and drying to obtain yellow leaf-shaped crystals, namely the nitrogenous carboxylic acid transition metal complex.
3. The method according to claim 2, wherein the molar ratio of zinc nitrate, triphenylamine 4,4',4 "-tricarboxylic acid, and 4,4' -bipyridine of S1 is 5:2:3; the volume ratio of the N, N-dimethylformamide to the N, N-dimethylacetamide in the mixed solvent is 2:1; the dosage ratio of the zinc nitrate to the N, N-dimethylacetamide is 0.1mmol:1mL.
4. The process according to claim 2, wherein the nitrogen-containing carboxylic acid transition metal complex in S2 has a specific surface area of 41.6m 2 /g～42.9m 2 And/g, the average pore diameter is 3.5 nm-4.2 nm.
5. Use of the nitrogen-containing carboxylic acid transition metal complex as claimed in claim 1, wherein the nitrogen-containing carboxylic acid transition metal complex is used for adsorption separation of gases.
6. The use according to claim 5, wherein the gas is CO 2 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310103899.9A CN116284063A (en) | 2023-02-13 | 2023-02-13 | Nitrogen-containing carboxylic acid transition metal complex and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310103899.9A CN116284063A (en) | 2023-02-13 | 2023-02-13 | Nitrogen-containing carboxylic acid transition metal complex and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116284063A true CN116284063A (en) | 2023-06-23 |
Family
ID=86823126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310103899.9A Pending CN116284063A (en) | 2023-02-13 | 2023-02-13 | Nitrogen-containing carboxylic acid transition metal complex and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116284063A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116813928A (en) * | 2023-06-29 | 2023-09-29 | 延安大学 | Nitrogen-containing carboxylic acid transition metal macroporous complex and preparation method and application thereof |
-
2023
- 2023-02-13 CN CN202310103899.9A patent/CN116284063A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116813928A (en) * | 2023-06-29 | 2023-09-29 | 延安大学 | Nitrogen-containing carboxylic acid transition metal macroporous complex and preparation method and application thereof |
| CN116813928B (en) * | 2023-06-29 | 2023-12-12 | 延安大学 | Nitrogen-containing carboxylic acid transition metal macroporous complex and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110496604B (en) | Cobalt-nickel bimetallic organic framework carbon dioxide adsorption material and preparation method and application thereof | |
| CN106699817B (en) | A kind of preparation method and applications of metal-organic framework material | |
| Xie et al. | Synthesis, characterization and experimental investigation of Cu-BTC as CO2 adsorbent from flue gas | |
| CN103435620B (en) | Porous copper organic framework material for CO2 adsorption and separation and preparation method of porous copper organic framework material | |
| CN106588960B (en) | A kind of metal-organic framework material and preparation method thereof for effective carbon-dioxide/nitrogen selective separation absorption | |
| KR20140111549A (en) | Carbon dioxide gas adsorbent comprising zeolite and methods for preparing the same | |
| Fan et al. | Constructing a robust gigantic drum-like hydrophobic [Co 24 U 6] nanocage in a metal–organic framework for high-performance SO 2 removal in humid conditions | |
| CN116284063A (en) | Nitrogen-containing carboxylic acid transition metal complex and preparation method and application thereof | |
| CN115181278B (en) | Preparation method and application of cobalt-based metal organic framework | |
| Mu et al. | Lanthanide contraction effects on the structures, thermostabilities, and CO 2 adsorption and separation behaviors of isostructural lanthanide–organic frameworks | |
| CN110776522B (en) | Copper metal organic framework material and preparation method thereof, gas capture method and gas separation method | |
| CN112827470A (en) | Selective air water-absorbing MOFs material with high stability and preparation method thereof | |
| CN115536857A (en) | Zinc-organic framework material for selectively adsorbing carbon dioxide and synthesis method | |
| CN109232226B (en) | Microporous metal organic framework material and preparation method and application thereof | |
| CN109485870B (en) | Stable porous cobalt complex, preparation method thereof and application thereof in adsorption and separation of gas micromolecules | |
| CN110563957B (en) | Preparation method and application of three-dimensional iron-based metal-organic framework | |
| CN108659234B (en) | Hexagonal cerium-based organic framework compound single crystal and preparation method thereof | |
| CN110040714A (en) | A kind of absorption carbon dioxide nitrogen phosphorus doping porous carbon materials and preparation method thereof | |
| Du et al. | Heterocycles for direct air capture and MOFs prepared from CO 2 utilization | |
| CN116376037B (en) | Preparation method and application of microporous zirconium-based metal organic framework material | |
| CN114989442B (en) | For CO 2 Preparation method of adsorption-captured ultra-microporous porous coordination polymer | |
| CN111004398B (en) | Microporous Cu-MOF material and preparation method and application thereof | |
| CN114849652A (en) | Activated carbon-encapsulated imidazole metal organic framework composite material with high gas separation selectivity and preparation method thereof | |
| CN110951085B (en) | Preparation of Cd-MOF and application of Cd-MOF in fluorescent recognition of DMSO and capture of CO2In (1) | |
| CN116003815B (en) | Microporous MOFs material ZnAtzCO constructed by carbonate 3 Is used for preparing and application in carbon dioxide/nitrogen separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |