CN109608652B - MOFs crystal material and preparation and application thereof - Google Patents
MOFs crystal material and preparation and application thereof Download PDFInfo
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Abstract
The application discloses an MOFs crystal material, which has a chemical formula shown in a formula I, wherein M is Zn and/or Cd; l represents a ligand having a chemical formula shown in formula II, wherein R in the formula II comprises at least one alkylene; BDC is terephthalate. The MOFs crystal material provided by the application is superior to acetylene in adsorption of carbon dioxide, so that the process of desorbing acetylene is omitted, energy is saved, the acetylene is convenient to desorb, a good separation effect is achieved on carbon dioxide and acetylene, and the synthesis process of the material can be controlled.
Description
Technical Field
The application relates to an MOFs crystal material and preparation and application thereof, belonging to the field of photocatalysis.
Background
Acetylene is an important industrial raw material, the current industrial preparation methods of acetylene mainly comprise a calcium carbide method and a natural gas method, and the acetylene prepared by the two methods contains carbon dioxide impurities.
The adsorption separation of acetylene and carbon dioxide by using the porous material can reduce energy consumption and environmental pollution. The MOFs materials show superior separation effects compared to conventional porous materials such as zeolite, carbon molecular sieve and mesoporous silica. However, because of the very similar physicochemical properties of carbon dioxide and acetylene, currently discovered MOFs materials capable of separating these two gases are extremely rare, most of which show that acetylene adsorbs more than carbon dioxide, whereas carbon dioxide adsorbs better than acetylene in only a few cases. Obviously, the process of desorbing acetylene can be reduced by directly removing carbon dioxide from the mixed gas, so that the energy is saved and the convenience is realized, but the design of the existing 6 cases of the materials is uncontrollable, the maximum ratio of the adsorption amount of the carbon dioxide to the adsorption amount of the acetylene is 6.4 under the condition of 273K and 1bar, and the separability is low. Therefore, the controllable synthesis of MOFs materials with carbon dioxide adsorption superior to acetylene and the improvement of the separation effect become research hotspots in the field of material chemistry.
Disclosure of Invention
According to one aspect of the application, the MOFs crystal material is provided, the adsorption of the crystal material to carbon dioxide is superior to the adsorption to acetylene, the process of desorbing acetylene is omitted, so that the energy is saved, the acetylene and the carbon dioxide are separated well, and the synthesis process of the material can be controlled.
A MOFs crystalline material having the formula:
[M5(L)2(BDC)4(OH)2]·nH2O
formula I
Wherein M is Zn and/or Cd;
l represents a ligand having the formula shown in formula II:
r in the formula II is at least one selected from alkylene;
BDC is terephthalate.
The MOFs crystal material provided by the application is a porous material for gas storage and separation, and has photochromic performance at room temperature. The crystal material has controllable synthesis and good separation effect of carbon dioxide and acetylene mixed gas. The L ligand in the application is viologen onium salt, has photochromic performance, the electric field gradient of the ligand is favorable for the adsorption of carbon dioxide, and the torsion angle between pyridine rings of the photochromic ligand is reduced, which is favorable for the increased porosity. Meanwhile, the addition of the auxiliary ligand BDC can maintain the electric field gradient of the MOFs material after photochromism. Thus, the adsorption of carbon dioxide by the MOF material after photochromism is improved, and the adsorption of acetylene is reduced, so that the adsorption value ratio of the two gases is increased.
Specifically, R may be C1～6Alkylene, or benzyl, or a benzylidene group, preferably, R is p-benzylidene.
When R is p-phenylene, the structure of the ligand L is shown as follows:
n may be any number, for example n may be 9.
The MOFs crystal material can be bulk crystals or crystal powder.
Optionally, the MOFs crystal material belongs to the P-1 space group of the triclinic system.
Optionally, the crystallographic data of the MOFs crystal material is:
preferably, the unit cell parameters of the MOFs crystal material are:
α＝104.557(3)–105.557(3)°，β＝103.252(3)–104.252(3)°，
γ＝95.979(3)–96.979(3)°；
optionally, when M is Zn, the crystallographic data of the MOFs crystal material is:
optionally, when M is Cd, the crystallographic data of the MOFs crystal material is:
optionally, the MOFs crystal material is a photochromic material.
The application provides an MOFs crystal material, which has the following structure: zn or Cd ions are bridged by two ligands to form a three-dimensional framework structure with triple overlapping, the structure is provided with one-dimensional holes, and guest molecules such as water or other solvent molecules are filled in the holes.
Specifically, as shown in fig. 1, M is Zn ion, R is p-phenylene group, BDC is terephthalate. And the L ligand is provided with two free ends, one free end is provided for N in the pyridine ring at the end part, the other free end is provided for carboxylate radical, and the two free ends are respectively connected with Zn ions in two small ring structures, so that a closed large ring structure is formed. One of the small ring structures is an octagonal structure formed by enclosing 2 terephthalic acid provided with a carboxylate radical and 2 Zn ions, and the 2 Zn ions are shared by two sets of octagonal structures. The other small ring structure is a structure in which 2 terephthalic acids respectively provide another carboxylate radical and are surrounded with 3 Zn ions to form an 8 shape, in the 8-shaped structure, the connecting point of a double ring is 1 Zn ion, and the other 2 Zn ions are respectively positioned on the ring frame of the double ring. N in the pyridine ring at the end of the L ligand is connected with Zn in the octagonal structure, and O in the carboxylate radical of the L ligand is connected with Zn on a double-ring frame in the 8-shaped structure.
Figure 1 shows a three-dimensional frame structure formed by overlapping 3 sets of the large ring structures. In the large ring structure, one side of the frame is arranged according to the sequence of an octagonal structure, terephthalic acid, an 8-shaped structure, terephthalic acid and an octagonal structure, the other side of the frame is reversely arranged according to the sequence of the 8-shaped structure, the terephthalic acid, the octagonal structure, the terephthalic acid and the 8-shaped structure to form a large ring, and an L ligand is connected between the 8-shaped structure and the octagonal structure in the middle of the large ring.
Different large ring structures are oppositely and alternately overlapped together, as shown in figure 1, one side of the adjacent first large ring is arranged according to the sequence of an octagonal structure, terephthalic acid, an 8-shaped structure, terephthalic acid and an octagonal structure; one side of the adjacent second large ring is reversely arranged according to the sequence of the 8-shaped structure, the terephthalic acid, the octagonal structure, the terephthalic acid and the 8-shaped structure; one side of the adjacent third large ring is repeatedly arranged on one side of the first large ring according to the order of the octagonal structure, the terephthalic acid, the 8-shaped structure, the terephthalic acid and the octagonal structure, so that a three-fold overlapped three-dimensional frame structure is formed. The gaps between the large ring structures are one-dimensional holes, and the gaps are filled with oxygen ions.
According to another aspect of the present application, there is also provided a method for preparing any one of the above MOFs crystal materials, at least comprising the steps of:
a) obtaining a ligand L: the synthesis of the ligands is improved on the basis of known methods (ref. Helvetica Chimica Acta,2005,88, 3200).
b) Adjusting the pH of a raw material containing a ligand L, M source, terephthalate and water to 8-9, placing the raw material in a closed container, and crystallizing the raw material for 2-3 days at 80-120 ℃ to obtain the MOFs crystal material.
The MOFs crystal material is a material before photochromism and has the function of storing gas. For example, a mixture of carbon dioxide and acetylene may be stored.
Specifically, in step (a), the preparation method of the ligand L may be any suitable method in the prior art, and the application is not strictly limited. Taking R in the ligand L as p-phenylene as an example, dinitrochlorobenzene and 4, 4' -bipyridine are preferably added into a 100mL round-bottom flask according to the ratio of 1:1, about 20-40 mL of acetone is added, and the reflux reaction is carried out for one day at the temperature of 60 ℃. Filtering, washing the obtained solid powder with diethyl ether for 3 times to obtain an intermediate; then adding the obtained intermediate and p-aminobenzoic acid into a 100mL round-bottom flask according to the ratio of 1:1.5, adding about 20-40 mL of ethanol, and carrying out reflux reaction at 90 ℃ for one day. Cooling, adding a proper amount of triethylamine and stirring until beige precipitate is generated, filtering, and washing the obtained solid powder with diethyl ether for 3 times to obtain the ligand L.
Specifically, firstly, a ligand L with photochromic performance is designed and synthesized; and adding M source, ligand L and terephthalate into water, uniformly mixing, adjusting the pH value to 8.0-9.0 by using alkali liquor, putting into a hydrothermal tank, putting into an oven, adjusting the temperature to 80-120 ℃ for crystallization, crystallizing for 2-3 days, taking out after the reaction is finished, and cooling to room temperature to obtain the MOFs crystal material.
Optionally, the M source in step b) is at least one selected from zinc nitrate, zinc chloride, cadmium nitrate and cadmium chloride;
in the step b), the pH value of the raw material containing the ligand L, M source, terephthalate and water is adjusted to 8-9 by using sodium hydroxide.
The MOFs crystal material is a photochromic material obtained after being irradiated by light.
Preferably, a xenon lamp with the wavelength of 200-450 nm is adopted for irradiation for 0.5-2 h.
The application also provides an application of any one of the MOFs crystal materials and the photochromic material in storage and/or separation of carbon dioxide and acetylene.
Specifically, the prepared MOFs crystal material is used for adsorbing the carbon dioxide and acetylene mixed gas so as to store the mixed gas in the MOFs crystal, then the crystal is placed under a xenon lamp for irradiation for a period of time, for example, 1 hour, so that a photochromic crystal can be obtained, and the ratio of the adsorption amount of the MOFs crystal to the carbon dioxide and the acetylene before and after photochromism is changed, so that the carbon dioxide and the acetylene are separated.
The beneficial effects that this application can produce include:
1) the MOFs crystal material provided by the application has the advantages that the ratio of the adsorption capacity of the MOFs crystal material to carbon dioxide and acetylene is 7.1 after illumination under the conditions of 273K and 1bar, and therefore the material has a good separation effect.
2) The MOFs crystal material provided by the application can adsorb carbon dioxide more than acetylene, so that the process of desorbing acetylene is reduced, and the MOFs crystal material is more energy-saving and convenient.
3) The method for preparing the MOFs crystal material provided by the application enables the synthesis process of the MOFs crystal material to be controlled.
Drawings
FIG. 1 shows sample CI-1#In (1) [ Zn ]5(L)2(BDC)4(OH)2]n·9nH2A schematic three-dimensional structure of O;
FIG. 2 shows sample CI-1#In (1) [ Zn ]5(L)2(BDC)4(OH)2]n·9nH2A powder X-ray diffraction pattern of O;
FIG. 3 shows sample CI-1#In (1) [ Zn ]5(L)2(BDC)4(OH)2]n·9nH2Adsorption patterns of O on carbon dioxide and acetylene before and after illumination.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
EXAMPLE 1 preparation of ligand L
The preparation process comprises the following steps: dinitrochlorobenzene and 4, 4' -bipyridine were first added in a 1:1 ratio to a 100mL round-bottom flask, and about 30mL of acetone were added and reacted at 60 ℃ under reflux for one day. Filtering to obtain solid powderWashing with ether for 3 times to obtain an intermediate; then, the obtained intermediate and p-aminobenzoic acid were added to a 100mL round-bottom flask at a ratio of 1:1.5, and about 30mL of ethanol was added, followed by reflux reaction at 90 ℃ for one day. Cooling, adding a proper amount of triethylamine and stirring until beige precipitate is generated, filtering, and washing the obtained solid powder with diethyl ether for 3 times to obtain the ligand. This sample was recorded as: l-1#At L-1#Wherein R is p-phenylene.
The preparation process comprises the following steps: halogenated hydrocarbon acid and 4, 4' -bipyridine were added in a ratio of 1:1 to a 100mL round-bottom flask, and about 35mL of acetonitrile was added and reacted at 70 ℃ under reflux for one day. Filtration and washing of the solid powder obtained with ether 3 times gave the ligand, which sample was recorded as: l-2#At L-2#Wherein R is an alkylene group.
The preparation process comprises the following steps: p-halomethylbenzoic acid and 4, 4' -bipyridine were added in a 1:1 ratio to a 100mL round-bottomed flask, and about 35mL of acetonitrile was added and reacted at 70 ℃ under reflux for one day. Filtration and washing of the solid powder obtained with ether 3 times gave the ligand, which sample was recorded as: l-3#In L-3#In the formula, R is benzyl.
EXAMPLE 2 preparation of MOFs crystalline Material
Zinc nitrate hexahydrate (1189mg), L-1#Preparing a ligand (138mg) and sodium terephthalate (210mg), adding 10 ml of water, stirring uniformly, adjusting the pH value to 8.0 by using a 0.2M sodium hydroxide aqueous solution, filling the mixture into a 20 ml polytetrafluoroethylene hydrothermal tank, putting the polytetrafluoroethylene tank into an oven, heating the polytetrafluoroethylene tank to 100 ℃, preserving heat for 2 days, taking out the polytetrafluoroethylene tank, and naturally cooling the polytetrafluoroethylene tank to room temperature to obtain the chemical formula [ Zn ]5(L)2(BDC)4(OH)2]·nH2MOFs crystals of O, denoted as CI-1#。
Zinc nitrate hexahydrate (1189mg), L-2#Preparing a ligand (138mg) and sodium terephthalate (210mg), adding 10 ml of water, stirring uniformly, adjusting the pH value to 9.0 by using a 0.2M sodium hydroxide aqueous solution, filling the mixture into a 20 ml polytetrafluoroethylene hydrothermal tank, putting the polytetrafluoroethylene tank into an oven, heating the tank to 80 ℃, preserving heat for 2 days, taking out the polytetrafluoroethylene tank, and naturally cooling the polytetrafluoroethylene tank to room temperature to obtain a chemical formula [ Zn ]5(L)2(BDC)4(OH)2]·nH2MOFs crystals of O, denoted as CI-2#。
Zinc nitrate hexahydrate (1189mg), L-3#Preparing a ligand (138mg) and sodium terephthalate (210mg), adding 10 ml of water, stirring uniformly, adjusting the pH value to 8.0 by using a 0.2M sodium hydroxide aqueous solution, filling the mixture into a 20 ml polytetrafluoroethylene hydrothermal tank, putting the polytetrafluoroethylene tank into an oven, heating to 90 ℃, preserving heat for 2 days, taking out the polytetrafluoroethylene tank, and naturally cooling to room temperature to obtain a chemical formula [ Zn ]5(L)2(BDC)4(OH)2]·nH2MOFs crystals of O, denoted as CI-3#。
Cadmium nitrate tetrahydrate (1234mg), L-1#Preparing a ligand (138mg) and sodium terephthalate (210mg), adding 10 ml of water, stirring uniformly, adjusting the pH value to 9.0 by using a 0.2M sodium hydroxide aqueous solution, putting into a 20 ml polytetrafluoroethylene hydrothermal tank, putting into an oven, heating to 110 ℃, preserving heat for 3 days, taking out, naturally cooling to room temperature to obtain a chemical formula of [ Cd [ ]5(L)2(BDC)4(OH)2]·nH2MOFs crystals of O, denoted CII-1#。
Cadmium nitrate tetrahydrate (1234mg), L-2# ligand (138mg) and sodium terephthalate (210mg) are mixed, 10 ml of water is added and stirred uniformly, the pH value is adjusted to 9.0 by using a sodium hydroxide aqueous solution with the concentration of 0.2M, the mixture is put into a polytetrafluoroethylene hydrothermal tank with the volume of 20 ml, the polytetrafluoroethylene hydrothermal tank is put into an oven and heated to 80-120 ℃, the temperature is kept for 3 days, the polytetrafluoroethylene aqueous solution is taken out and naturally cooled to room temperature, and the chemical formula [ Cd5(L)2(BDC)4(OH)2]·nH2MOFs crystals of O, denoted CII-2#。
Cadmium nitrate tetrahydrate (1234mg), L-3#Preparing a ligand (138mg) and sodium terephthalate (210mg), adding 10 ml of water, stirring uniformly, adjusting the pH value to 8.0 by using a 0.2M sodium hydroxide aqueous solution, putting into a 20 ml polytetrafluoroethylene hydrothermal tank, putting into an oven, heating to 120 ℃, preserving heat for 3 days, taking out, naturally cooling to room temperature to obtain a chemical formula of [ Cd [ ]5(L)2(BDC)4(OH)2]·nH2MOFs crystals of O, denoted CII-3#。
EXAMPLE 3 structural characterization of the samples
Sample CI-1#～CⅠ-3#、CⅡ-1#～CⅡ-3#The phase analysis (XRD) of the milled X-ray powder diffractometer was performed on a MiniFlex type ii X-ray diffractometer from Rigaku, Cu target, K α radiation source (λ 0.154184 nm).
Sample CI-1#～CⅠ-3#、CⅡ-1#～CⅡ-3#The X-ray single crystal diffraction of (2) was carried out on a Mercury CCD-type single crystal diffractometer, Mo target, K α radiation source (. lamda. 0.07107nm), test temperature 293K and structure analysis thereof by Shelxtl97, using CI-1#As a typical representative, when the XRD diffraction theory pattern calculated by introducing the single crystal diffraction structure data cif file into the software mercury3.5 is compared with the experimentally measured XRD diffraction pattern as shown in fig. 2, it can be seen that the XRD diffraction pattern obtained by fitting the single crystal data is highly consistent with the experimentally measured XRD diffraction pattern, which proves that the obtained sample is a high purity and high crystallinity sample.
The X-ray powder diffraction and polycrystalline diffraction results show that:
CⅠ-1#～CⅠ-3#、CⅡ-1#～CⅡ-3#(chemical formula [ M ]5(L)2(BDC)4(OH)2]·nH2O) all belong to the triclinic P1 space group. And metal ions (Zn ions or Cd ions) are formed and bridged by two ligands to form a three-dimensional framework structure with triple overlapping, one-dimensional holes are formed in the structure, and oxygen ions are filled in the holes. Wherein, the compound is represented by the formula II-1#The specific structure is shown in figure 1 as a typical representation.
Specifically, CI-1#～CⅠ-3#Has unit cell parameters of
b＝1
α＝104.557(3)–105.557(3)°，β＝103.252(3)–104.252(3)°，γ＝95.979(3)–96.979(3)°；
Z＝1。CⅡ-1#～CⅡ-3#The unit cell parameters are as follows:
α＝104.127–105.127°，β＝103.342–104.342°，γ＝96.019–97.019°，Z＝1。
example 4 preparation of post-photochromic Material
Respectively mixing them#～CⅠ-3#、CⅡ-1#～CⅡ-3#Placing the sample under a xenon lamp with the wavelength of 200-450 nm for irradiating for 1h to obtain photochromic material samples which are respectively marked as CI-1#-L～CⅠ-3#-L、CⅡ-1#-L～CⅡ-3#-L。
Example 5 carbon dioxide and acetylene adsorption ratio test experiment
Respectively adding 100-150 mg of CI-1#～CⅠ-3#、CⅡ-1#～CⅡ-3#、CⅠ-1#-L～CⅠ-3#-L、CⅡ-1#-L～CⅡ-3#After the crystal or powder of-L is activated at a temperature of about 80 ℃ under vacuum for about 16 hours, isothermal adsorption and desorption properties of carbon dioxide and acetylene before and after photochromism of the crystal compound under 273K conditions are tested by an adsorption system of ASAP 2020. And (3) plotting the pressure as an abscissa and the measured adsorption performance as an ordinate to obtain adsorption values of different gases under the conditions of 273K and 1bar, and judging the storage capacity of the MOFs crystal material on carbon dioxide and acetylene gases and the separation capacity of the MOFs crystal material on the carbon dioxide and acetylene gases.
The results show that: light (es)Sample CI-1 before discolouration#～CⅠ-3#、CⅡ-1#～CⅡ-3#And sample CI-1 after photochromism#-L～CⅠ-3#-L、CⅡ-1#-L～CⅡ-3#both-L can better adsorb/separate carbon dioxide and acetylene. Wherein, the separation performance of the sample after photochromism on carbon dioxide and acetylene is better than that of the sample before photochromism.
With CI-1#And CI-1#-L is a typical representation and FIG. 3 is [ Zn ]5(L)2(BDC)4(OH)2]·nH2Adsorption pattern of O, fig. 3 shows: CI-1#The photochromic material has better separation performance on carbon dioxide and acetylene gas. As shown in table 1: CI-1#The ratio of the adsorption amount of the crystal material to carbon dioxide and acetylene is increased from 5.0 before color change to 7.1 after color change.
TABLE 1 CI-1 at 273K, 1bar#Adsorption capacity of polycrystalline material to carbon dioxide and acetylene before and after discoloration
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (9)
1. A MOFs crystalline material having the formula:
[M5(L)2(BDC)4(OH)2]·nH2O
formula I
Wherein M is Zn and/or Cd;
l represents a ligand having the formula shown in formula II:
r in the formula II is at least one selected from alkylene;
BDC represents terephthalate;
the crystallographic data of the MOFs crystal material are as follows:
2. a MOFs crystalline material according to claim 1, wherein R in formula II is p-phenylene.
3. MOFs crystal material according to claim 1 or 2, characterized in that it belongs to the P-1 space group of the triclinic system.
4. Crystalline MOFs material according to claim 3,
when M is Zn, the crystallographic data of the MOFs crystal material are as follows:
when M is Cd, the crystallographic data of the MOFs crystal material are as follows:
5. the MOFs crystal material of claim 1, wherein the MOFs crystal material is a photochromic material.
6. A process for the preparation of crystalline materials of the MOFs according to any of the claims 1 to 5, characterized in that it comprises at least the steps of:
a) obtaining a ligand L;
b) and (3) adjusting the pH of the raw materials containing the ligand L, M source, terephthalate and water to 8-9, placing the raw materials in a closed container, and crystallizing the raw materials at the temperature of 80-120 ℃ for 2-3 days to obtain the MOFs crystal material.
7. The method of claim 6, wherein the M source of step b) is selected from at least one of zinc nitrate, zinc chloride, cadmium nitrate, cadmium chloride;
in the step b), the pH value of the raw material containing the ligand L, M source, terephthalate and water is adjusted to 8-9 by using sodium hydroxide.
8. The photochromic material obtained by irradiating the MOFs crystal material of any one of claims 1 to 4 with light.
9. Use of the MOFs crystal material according to any one of claims 1 to 5 or the photochromic material according to claim 8 for storing and/or separating carbon dioxide and acetylene.
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