CN113336955B - Hollow rare earth-based MOFs material based on solvothermal method - Google Patents
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Abstract
The invention discloses a hollow rare earth-based MOFs material based on a solvothermal method. Mixing lanthanide metal salt, 1,3, 5-benzene tricarboxylic acid (H) 3 BTC) and thiophene-2, 5-dicarboxylic acid (H) 2 TDC) are respectively placed in a reactor, and a solvent is added for dissolution; mixing the three solutions prepared in the step 1), and heating and reacting in a closed system; and finally, carrying out solid-liquid separation on the product after the reaction, and washing the obtained solid product to obtain the hollow rare earth-based MOFs material. The process is carried out with H 2 TDC is a reaction auxiliary agent and takes H 3 BTC is an organic ligand, lanthanide metals are taken as centers (terbium ions and europium ions), and the novel hollow spherical lanthanide metal-organic framework material is synthesized by a solvothermal method.
Description
Technical Field
The invention relates to the field of sensor material preparation.
Background
Hollow MOFs have the characteristics of effectively improving the adsorption, filtration, diffusion and transfer of molecules through porous shells due to the inherent porous structure, excellent designability and flexibility. At present, the preparation methods of hollow MOFs include template guiding method, interface guiding method, partial etching method, etc., but still have the following disadvantages:
(1) The template method requires precise control of the form and surface characteristics of the template, the steps are complicated, the problem of the number and quality of the template can cause irregular growth of the hollow MOFs, and the hollow structure is easy to collapse after the template is removed, so that the performance of the hollow MOFs is influenced.
(2) At present, the size and shape of bubbles or liquid drops are difficult to control by an interface induction method (a gas-liquid interface method), so that the morphology of the prepared MOFs material is difficult to control. In addition, the interface characteristics, the types and concentrations of organic ligands and solvents, and the like in the interface induction method have a significant influence on the structure, morphology, and robustness of the hollow MOFs, and may result in the occurrence of non-hollow structures.
(3) The partial etching method is based on competitive coordination, polyoxometallate (POM) molybdate and Thioacetamide (TAA) are used as competitive reagents, and the Co-BTC microcapsule is prepared by the partial etching method. The method not only needs to be modified/deformed in the later period to form the hollow structure, but also controls the concentration of competitive reagents, which is a key and difficult point for preparing hollow MOFs.
Based on the above analysis, the existing hollow MOFs preparation method has disadvantages, and a simple, economical and easy-to-operate hollow MOFs preparation method is needed.
Disclosure of Invention
The invention aims to provide a hollow rare earth-based MOFs material based on a solvothermal method, which is characterized in that the preparation method of the material comprises the following steps:
1, mixing lanthanide metal salt and 1,3, 5-benzene tricarboxylic acid (H) 3 BTC) and thiophene-2, 5-dicarboxylic acid (H) 2 TDC) are respectively placed in a reactor, and a solvent is added for dissolution;
mixing the three solutions prepared in the step 1), and heating the mixture in a closed system for reaction;
and 3, carrying out solid-liquid separation on the product after the reaction, and washing the obtained solid product to obtain the hollow rare earth-based MOFs material.
Further, in step 1), the lanthanide is a trivalent rare earth metal, and the acid radical is an acid radical capable of fusing rare earth ions.
Further, in step 1), the lanthanide metal is terbium, europium, praseodymium, samarium or cerium, and the acid radical is nitrate radical, acetate radical, sulfate radical or hydrochloride radical.
Further, in step 1), the metal salt is selected from: terbium nitrate hexahydrate [ Tb (NO) 3 ) 3 ·6H 2 O, europium nitrate hexahydrate [ Eu (NO) 3 ) 3 ·6H 2 O ], and other soluble rare earth salts and mixtures thereof. The metal salt is selected from: terbium nitrate hexahydrate [ Tb (NO) 3 ) 3 ·6H 2 O, europium nitrate hexahydrate [ Eu (NO) 3 ) 3 ·6H 2 O ], and other soluble rare earth salts and mixtures thereof.
Further, in step 1), the solvent is N, N-dimethylformamide (DMF, AR).
In step 1), a lanthanide metal salt, H 3 BTC、H 2 The mass ratio of the TDC is: 1: 1-4.
Further, in the step 2), heating and reacting in a high-pressure reaction kettle; the reaction temperature is 80-180 ℃, and the reaction time is 24-72 h.
Further, in the step 3), a centrifugal tube is adopted for separation, and DMF is used for centrifugal washing; after washing, the product obtained is dried.
Further, H 3 BTC and DMF participate in lanthanide metal cation coordination; h 2 TDC is used as a reaction auxiliary agent and is not coordinated with lanthanide metal cations; eventually a hollow sphere structure centered on the lanthanide metal cation is formed.
Further, in the step 2), metal salt formed by two lanthanide metals is adopted, and finally the hollow bimetal MOFs material is obtained.
Furthermore, the two metals have different characteristic emission peaks, and the emission wavelength of the MOFs is adjusted by adjusting the proportion of the two metals.
The technical result of the invention is undoubtedly that the method takes H 2 TDC is a reaction auxiliary agent and is H 3 BTC is an organic ligand, lanthanide metal is taken as a center (terbium ion and europium ion), and a novel hollow spherical lanthanide metal-organic is synthesized by a solvothermal methodA frame material.
Drawings
FIG. 1: (a) a route for the synthesis of Tb-MOF; (b) a coordination environment for the Tb atom; (c) bond length around Tb atom in binuclear structure; (d) a process of forming a three-dimensional framework of Tb-MOF. FIGS. 2 (a) and (b) respectively show Tb 1-x /Eu x XRD, TG pattern of MOF (x =0,0.02,0.04,0.06, 1) sample.
FIG. 3 hollow Tb-MOF Synthesis Process (a) SEM image taken during hollow Tb-MOF formation; (b) schematic diagram of hollow Tb-MOF formation process.
FIG. 4 (a) No H addition 2 SEM image of Tb-MOF sample of TDC; (c) Addition of H 2 SEM image of Tb-MOF sample of TDC; note: other reaction conditions are consistent; (c) The figure shows the addition of H 2 A TEM image of the TDC; (d) (e), (f) and (g) are Mapping of C, O, N and Tb elements respectively; (f) Is a line analysis chart of a Mapping chart of Tb elements
FIG. 5 (a) 1 And a 2 )、(b 1 And b 2 )、(c 1 And c 2 )、(d 1 And d 2 )、(e 1 And e 2 ) Respectively represent Tb 1-x /Eu x SEM pictures of samples of MOFs (x =0,0.02,0.04,0.06, 1), (f) Tb-MOFs made of directly mixed metals and organic ligands; (a) 1 、b 1 、c 1 、d 1 、e 1 ): ln-MOFs Overall SEM Picture (a) 2 、b 2 、c 2 、d 2 、e 2 ) Represents an enlarged SEM picture of a single sphere of Ln-MOF, and an inset shows a partial enlarged picture;
FIG. 6 (a), (b), (c), (d), (e), (f) and (g) each represents a ligand H 3 BTC and reaction auxiliary agent H 2 (ii) SEM image of hollow spheres of Tb-MOF for TDC species in a ratio of 1, 2; (h) Is ligand H 3 BTC and reaction auxiliary agent H 2 The amount of TDC substance is enlarged from the outer surface of the hollow sphere under 1.
FIG. 7 (a) H 3 BTC and H 2 The emission spectrums of Tb-MOFs of different proportions of TDC; (b) Tb 1-x /Eu x -emission spectrum of MOFs (x =0,0.02,0.04,0.06, 1).
FIG. 8 (a) Tb 1-x /Eu x -MOFs(x＝0,0.02,0.04,0.06, 1) color coordinate diagram of the material, inset Tb 1-x /Eu x -luminescence pattern of MOFs (x =0.02,0.04, 0.06) materials under 365nm uv lamp irradiation; (b) Tb 1-x /Eu x -MOFs (x =0,0.02,0.04,0.06, 1) material luminescence lifetime; (c) Tb 1-x /Eu x Of the MOFs (x =0.02,0.04, 0.06) 5 D 4 (Tb 3 + ) And 5 D 0 (Eu 3+ ) Comparison of life time of (1).
FIG. 9 (a) bar graph of the luminescence intensity at 545nm for Tb-MOFs in different metal ion aqueous solutions, inset: overall emission spectrogram; (b) Tb-MOFs at varying concentrations of Fe 3+ The inset is the emission spectrogram of a monitoring peak near 545 nm; (c) Luminescence intensity of Tb-MOF and Fe 3+ Relationship between concentrations (0-150. Mu.M), inset: luminescence intensity of Tb-MOF and low Fe 3 + Linear relationship between concentrations (0-10. Mu.M); (d) I of Tb-MOF in Water 0 I and Fe 3+ Relationship between concentrations (0-150. Mu.M), inset: I.C. A 0 I and low Fe 3+ Linear relationship between concentrations (0-8 μ M).
FIG. 10 (a) bar graph of maximum luminescence intensity of Tb-MOFs in DMF solution of different metal ions, inset: overall emission spectrogram; (b) Tb-MOFs at various concentrations of Fe 3+ Emission spectra in solution, inset is the emission spectra near the 545nm monitoring peak; (c) Tb-MOFs luminous intensity and Fe 3+ Relationship between concentrations (0-150. Mu.M), inset: tb-MOF luminescence intensity with low Fe 3+ Linear relationship between concentrations (0-10. Mu.M); (d) I of Tb-MOFs 0 I and Fe 3+ Relationship between concentrations (0-150. Mu.M), inset: i is 0 I and low Fe 3+ Linear relationship between concentrations (0-8 μ M).
FIG. 11 (a) Tb-MOFs and Tb-MOFs @ Fe 3+ XPS total spectrum of (a); (b) Tb-MOFs and Tb-MOFs @ Fe 3+ Tb3d diagram of (a); (c) Fe in water 3+ Ultraviolet-visible absorption spectrum of (1) and excitation spectrum of Tb-MOFs; (d) Tb-MOFs and Tb-MOFs @ Fe 3+ And (4) luminous life.
Fig. 12 (a) left: the luminous color of Tb-MOFs in water under 365nm light irradiation; and (3) right: under 365nm light irradiation, fe 3+ Adding the mixture into Tb-MOFs suspension; (b) left: fe 3+ Aqueous solution(ii) a And (3) right: fe with Tb-MOFs addition 3+ A solution; (c) left: tb-MOF powder; right adsorption of Fe 3+ The latter Tb-MOFs powder.
FIG. 13 (a) emission spectra of Eu-MOFs in a suspension of water with different metal ions; (b) overall emission spectra of Eu-MOFs in NB suspension liquids with different concentrations; (c) The relationship between the luminescence intensity of Eu-MOFs and the NB concentration (0-500 ppm), inset: a linear relationship between the luminescence intensity of Eu-MOFs and the low NB concentration (0-10 ppm); (d) I of Eu-MOFs 0 Linear relationship between/I and NB concentration (0-500 ppm).
FIG. 14 (a) ligand H 2 TDC and H 3 Schematic electronic structures of BTC and NB; (b) simplified schematic of LMET and Dexter-ET of ligand pair NB; (c) a response mechanism diagram of Eu-MOF to NB.
Detailed Description
The present invention will be further described with reference to the following examples, but it should be understood that the scope of the subject matter described above is not limited to the following examples. Various substitutions and modifications can be made without departing from the technical idea of the invention and the scope of the invention according to the common technical knowledge and the conventional means in the field.
Example 1:
a hollow rare earth-based MOFs material based on a solvothermal method is characterized in that the preparation method comprises the following steps:
1, weighing lanthanide metal salt and 1,3, 5-benzene tricarboxylic acid (H) according to the molar ratio in the table 1 3 BTC) and thiophene-2, 5-dicarboxylic acid (H) 2 TDC) are respectively placed in a reactor, and a DMF solvent (excess) is added to fully dissolve the substances;
TABLE 1 amounts of the substances
Mixing the three solutions prepared in the step 1), and heating the mixture in a closed system for reaction; the reaction temperature range is 150 ℃, and the reaction time is 72h.
And 3, carrying out solid-liquid separation on the product after the reaction, and washing the obtained solid product by adopting DMF (dimethyl formamide) to obtain the hollow rare earth-based MOFs material.
Example 2:
a hollow rare earth-based MOFs material based on a solvothermal method is characterized in that the preparation method comprises the following steps:
weighing two lanthanide metal salts and 1,3, 5-benzenetricarboxylic acid (H) according to the molar ratio in Table 1 3 BTC) and thiophene-2, 5-dicarboxylic acid (H) 2 TDC) are respectively placed in a reactor, and a DMF solvent (excess) is added to fully dissolve the substances;
the ratio of the two lanthanide metal salts is (1-x):x, x =0,0.02,0.04,0.06,1 (when x =0, it represents only one metal).
Mixing the three solutions prepared in the step 1), and heating the mixture in a closed system for reaction; the reaction temperature range is 150 ℃, and the reaction time is 72h.
And 3, carrying out solid-liquid separation on the product after the reaction, and washing the obtained solid product by adopting DMF (dimethyl formamide) to obtain the hollow rare earth-based MOFs material.
Example 3:
a hollow rare earth-based MOFs material based on a solvothermal method is characterized in that the preparation method comprises the following steps:
weighing terbium nitrate hexahydrate and 1,3, 5-benzenetricarboxylic acid (H) according to the molar ratio in Table 2 3 BTC) and thiophene-2, 5-dicarboxylic acid (H) 2 TDC) are respectively placed in a reactor, and a DMF solvent (excess) is added to fully dissolve the substances;
TABLE 2 amounts of the respective substances in the synthesis of Tb-MOF
Mixing the three solutions prepared in the step 1), and heating the mixture in a closed system for reaction; the reaction temperature range is 150 ℃, and the reaction time is 72h.
And 3, carrying out solid-liquid separation on the product after the reaction, and washing the obtained solid product by adopting DMF (dimethyl formamide) to obtain the hollow rare earth-based Tb-MOFs material.
Experimental part:
single crystal diffraction data were recorded at Ga K.alpha.using a Bruker D8 Advance X-ray diffractometer in Germany, and powder X-ray diffraction Patterns (PXRD) of samples were recorded at Cu K.alpha.using a PANALYTIC EMPYREan Series2 diffractometer from Cibach instruments systems Ltd, UK, in the range of 5-50 DEG 2 theta, with an operating voltage of 40kV, a current of 40mA, and step and scan speeds of 0.026 DEG and 7 DEG min, respectively -1 (ii) a Testing morphology and analyzing elements by using a Talos F200S field emission transmission electron microscope; observing the appearance of the sample by using a JSM-7800F field emission scanning electron microscope of Japan electronic Co Ltd; the TGA data of the sample is recorded by using a TGAQ-50 thermogravimetric analyzer of American TA company, wherein the temperature rise rate is 10 ℃/min under the nitrogen atmosphere, and the temperature range is 10-700 ℃; the excitation and emission spectra of the samples were recorded by a heliotropin F4600 fluorescence spectrophotometer. The luminescence lifetime and quantum yield were tested using an FLS980 transient spectrometer from Edinburgh. The absorption spectrum was measured by a Nippon Shimadzu UV spectrometer UV-3600.
Taking Tb-MOF obtained in example 3 as an example, the crystallographic data of Tb-MOF are shown in Table 3, and the key bond lengths and bond angles are shown in tables 4 and 5.
TABLE 3 crystallographic data of Tb-MOF
TABLE 4 partial bond lengths in the Tb-MOF crystal structure
TABLE 5 partial bond angles in Tb-MOF Crystal Structure
The single crystal analysis result shows that Tb-MOFs belongs to monoclinic system (monoclinic), space group is C2/C, and lattice parameter
H 3 BTC and DMF both participate in coordination to form Tb 3+ Three-dimensional MOFs structure as a center, and H 2 TDC has no Tb 3+ And (4) coordination. Each local asymmetric unit in the unit cell contains 1 Tb 3+ 4, H 3 BTC anions and 2 DMF molecules form a Tb dual-core structure by every two asymmetric units, and a stable three-dimensional structure is formed between every two dual-core structures by chain connection and fork layer connection. 4H 3 BTC anion and 2 DMF molecules with Tb 3+ The coordination environment of (A) is shown in FIG. 1, H 3 BTC has three carboxylic acid groups, and the coordination modes are respectively mu 2-eta 1: eta.1,. Eta.1 means that two carboxylic acid groups are bidentate and chelated at Tb respectively 3+ One carboxylic acid group being bridged to Tb 3+ Each H is illustrated 3 BTC is all linked with 4 Tb 3+ And (4) coordinating. DMF molecular monodentate coordination Tb 3+ Tb01, as shown in FIG. 1 (b), coordinates in 8 coordination modes with 8 surrounding oxygen atoms, 6 of which are derived from 3H 3 BTC,2 oxygen atoms from DMF, from H 3 O002 and O005 in BTC 1 adopt asymmetric chelation and Tb 3+ Coordination, having a bonding length of Tb-O of each
And
the key angle of Tb-O-Tb is 54.30 (12) °; h 3 O009 and O006 adopt symmetry in BTC 2Chelation with Tb 3+ Coordination, tb-O has a bond length of
And
as shown in fig. 1 (c). The bonding angle of Tb-O-Tb was 53.61 (14) °, H 3 BTC 3 and H 3 O003 and O004 in BTC 4 proceed with Tb by bridging 3+ Coordination having a bonding angle of Tb-O of each
And
o007 and O008 monodentate Tb from DMF1 and DMF2 3+ The bonding angles of Tb-O are respectively
And
the bond angle of O-Tb-O in the whole coordination is in the range of 53.61 (14) ° -156.56 (14) °. As shown in FIG. 1 (d), tb-MOF can be regarded as H 3 BTC molecules and Tb form a chain-shaped dual-core structure, and the BTC molecules and Tb grow into a two-dimensional planar structure, and then pass through H 3 BTCs are cross-linked into a three-dimensional frame structure.
The Tb-MOF is used for researching the sensing performance of metal ions:
the Tb-MOFs of the single metal can respectively realize the Fe 3+ And sensitive detection of NB. Tb-MOFs on Fe in water 3+ The detection limit and the quenching constant of (2.05. Mu.M) and (0.058. Mu.M), respectively -1 。
2mg of Tb-MOFs powder was added to 2ml of 1X 10 powder -3 mol/L of M (NO) 3 ) x (M＝Fe 3+ ,Ca 2+ ,Bi 3+ ,Ba 2+ ,Ca 2+ ,Cr 3+ ,Co 2+ ,Mn 2+ ,Cu 2+ ,Zn 2+ ,NH 4 + ,Ag + ) Aqueous solution, ultrasoundDispersing and mixing uniformly, testing the luminescence spectrum in a quartz cuvette, and testing the sensing performance of Tb-MOFs to different ions. FIG. 9 (a) is a histogram of the luminescence intensity of Tb-MOF suspension containing different metal ions at 545nm, and the corresponding emission spectrum is shown in the inset, and the results show that different metal ions have different degrees of quenching effect on the luminescence of Tb-MOFs. Comparative finding of Fe 3+ The quenching effect on Tb-MOFs is strongest. To further explore the Tb-MOF vs. Fe 3+ Sensitivity of ion recognition, and experiments also research Fe with different concentrations 3+ (0, 0.5,1,2,4,6,8,10,20,30,50,70,90,120 and 150. Mu.M) luminescence response behavior to Tb-MOFs, the result is shown in FIG. 8 (b), and the inset is the emission spectrum around a wavelength of 545 nm. As a result, it was found that 3+ Increase in concentration, tb 3+ Gradually decreasing the emission peak intensity of Fe 3+ At a concentration of 150. Mu.M the luminescence was completely quenched. In FIG. 9 (b), each Fe at 545nm 3+ Luminous intensity of Tb-MOFs at concentration corresponding to Fe 3+ The concentrations were plotted as a fitted curve (FIG. 9 (c)). Fe 3+ The concentration is in the range of 0-150 μ M, and the luminous intensity of Tb-MOFs is dependent on Fe 3+ The increase in concentration decreases exponentially and satisfies the functional relationship y =526.8exp (-x/6.3) +1014.5exp (-x/89.9) -176.4, fitting parameter R 2 =0.9981. FIG. 9 (c) inset shows Fe 3+ The luminous intensity of Tb-MOFs and Fe with the concentration in the range of 0-10 μ M 3+ The concentration presents a good linear relation, satisfies y =1335.7-55.8x, and has linearity of R 2 =0.9974. According to the slope of the fit curve within 0-10 mu M and the detection limit calculation formula, the Tb-MOF to Fe can be calculated 3+ The detection limit of (2).
Here, N is Fe is not added 3+ Number of blank groups measured (N = 20), F 0 Is the luminous intensity of the sample in water, F is F 0 Average value of (1), S b (S b = 49.7) standard deviation of 20 blank groups, S is Fe in the inset of fig. 9 (c) 3+ The slope of the curve in the range of 0-10 μ M concentration (S = 55.8). Substituting the above values to calculate Tb-MO in waterF sample to Fe 3+ The detection limit of (D) is about 2.05 mu M, which shows that the prepared Tb-MOF is opposite to Fe 3+ Has a lower detection limit. Detection of Fe by Tb-MOF 3+ The sensitivity of (D) can be analyzed by the Stern-Volmer equation
Wherein I 0 Is free of Fe 3+ The luminous intensity of Tb-MOF in water, I is the addition of Fe 3+ Luminescence intensity of the rear sample, [ M ]]Is corresponding to Fe 3+ Concentration of (A), K SV Is the quenching constant of the sample.
FIG. 9 (d) is Fe 3+ Concentration of Fe in the range of 0-150 μ M 3+ The Stern-Volmer curve of the Tb-MOF luminous intensity satisfies an exponential relation
Degree of fit is R 2 =0.9967. In Fe 3+ Concentration of Fe in the range of 0-10 μ M 3+ The Stern-Volmer curve satisfies the linear relationship y =0.98+0.07x, and the fitting degree is about R 2 =0.9887. Combining the Stern-Volmer equation, fe can be calculated 3+ Quenching constant on Tb-MOF was approximately K SV ＝0.058μM -1 . The Tb-MOF can well detect Fe in water 3+ 。
The experiment also further explores the sensing performance of Tb-MOFs on different metal ions in a DMF environment, and the result is shown in FIG. 10. FIG. 10 (a) is a bar graph of the luminescence intensity of Tb-MOFs at 545nm in DMF solution containing different metal ions, and the corresponding emission spectrum is shown in the inset, and the result shows that Fe is in the DMF system 3+ 、Zn 2+ 、Mn 2+ 、Cu 2+ 、Ag + 、Bi 3+ The equal amount has a certain quenching effect on the luminescence of Tb-MOFs, fe 3+ Has the strongest quenching capability, which indicates that Tb-MOFs can specifically recognize Fe in DMF 3+ . FIG. 10 (b) shows Tb-MOFs at different concentrations of Fe 3+ The emission spectrum in the solution is shown as an emission spectrum around 545nm in an inset, and the result shows that the emission spectrum is changed along with Fe 3+ The increase of the concentration gradually reduces the luminous intensity of Tb-MOFs. For each concentration of Fe 3+ Maximum luminous intensity of Tb-MOFs in solution and corresponding Fe 3+ The concentrations were curve-fitted (FIG. 10 (c)). Fe 3+ The concentration is in the range of 0-150 mu M, the luminous intensity of Tb-MOFs varies with Fe 3+ The increase in concentration decreases exponentially, satisfying the functional relationship y =633.1exp (-x/8.0) +396.0exp (-x/47.0) -8.4, with a degree of fit R 2 ＝0.9944，Fe 3+ The concentration is in the range of 0-10 mu M, the luminous intensity of the sample and Fe 3+ The concentration has good linear relation, satisfies y =999.6-56.4x, and has linearity of R 2 =0.9916. According to the detection limit formula, tb-MOF can be deduced to Fe in a DMF system 3+ Has a detection limit of about 0.80. Mu.M, i.e., tb-MOF for Fe in DMF 3+ There is still a lower detection limit. Fe 3+ Concentration in the range of 0-150. Mu.M, fe 3+ The Stern-Volmer curve satisfies the exponential relationship y =3.2exp (-x/-46.0) -1.9, with a degree of fit of about R 2 ＝0.9918。Fe 3+ Concentration in the range of 0-8. Mu.M, fe 3+ The Stern-Volmer curve satisfies the linear relation y =0.99+0.09x, and the linearity is about R 2 =0.9918 (fig. 10 (d)). According to the formula
Calculating Tb-MOF to Fe in DMF 3+ Has a quenching constant of about K SV ＝0.095μM -1 。
Example 4:
a hollow rare earth-based MOFs material based on a solvothermal method is characterized by comprising the following steps:
1, weighing europium nitrate hexahydrate and 1,3, 5-benzene tricarboxylic acid (H) according to the molar ratio in the table 2 3 BTC) and thiophene-2, 5-dicarboxylic acid (H) 2 TDC) are respectively placed in a reactor, and a DMF solvent (excess) is added to fully dissolve the substances;
TABLE 3 amounts of the respective substances in the Eu-MOF Synthesis
Mixing the three solutions prepared in the step 1), and heating the mixture in a closed system for reaction; the reaction temperature range is 150 ℃, and the reaction time is 72h.
And 3, carrying out solid-liquid separation on the product after the reaction, and washing the obtained solid product by adopting DMF (dimethyl formamide) to obtain the hollow rare earth-based Eu-MOFs material.
The Tb-MOFs and the Eu-MOFs of the single metal can respectively realize the Fe 3+ And sensitive detection of NB. Tb-MOFs on Fe in water 3+ The detection limit and the quenching constant of (2) were 2.05. Mu.M and 0.058. Mu.M, respectively -1 . The detection limit and quenching constant of Eu-MOFs for NB were about 1.653ppm and 0.048ppm, respectively -1 。
Research on luminescence sensing performance of Eu-MOFs:
2mg of Eu-MOFs powder is respectively added into 10 different liquids of 2mL of absolute ethyl alcohol (EtOH), absolute methanol (MeOH), dimethyl sulfoxide (DMSO), N-Dimethylacetamide (DMF), N-Dimethylformamide (DMA), isopropanol (IPA), tetrahydrofuran (THF), ethylene Glycol (EG), formaldehyde (CF) and NB, and the like, ultrasonic treatment is carried out for 10min to obtain uniformly dispersed suspension, and the luminescence spectrum of the suspension is measured in a quartz cuvette. FIG. 13 (a) and its inset show the emission spectra of Eu-MOFs in suspension with different solvent systems and the corresponding bar graphs of maximum luminescence intensity. As can be seen from the figure, the luminescence conditions of Eu-MOFs in different solvent systems are different, and particularly, after the Eu-MOFs is added into an NB solution, the luminescence is completely quenched, which shows that the Eu-MOFs can be used for sensitive detection of NB, and the Eu-MOFs have strong luminescence in MeOH and EtOH, so that EtOH is selected as an NB dissolving system in subsequent experiments to perform sensitive performance test of low-concentration NB.
To further investigate the quenching effect of NB on luminescence of Eu-MOFs samples, 2mL of NB solutions with concentrations of 0,1,2,4,6,8,10,30,50,70,90,120,150,200,300,400, and 500ppm were prepared, 2mg of dried Eu-MOFs were added to NB solutions with respective concentrations, and the emission spectra were measured after uniform ultrasonic dispersion (FIG. 13 (b)). As the concentration of NB increases, the luminescence intensity of Eu-MOFs gradually decreases, when the concentration of NB is 70ppm, the luminescence intensity is quenched by 62%, when the concentration of NB is 200ppm, the luminescence is quenched by 84%, and when the concentration of NB reaches 500ppm, the luminescence intensity is quenched by 93%, thus the Eu-MOFs prepared by design can be used as a good luminescence identification material for detecting NB.
FIG. 13 (c) shows the fitting result of a curve obtained by fitting the maximum value of the luminescence intensity of Eu-MOFs in NB solution of each concentration in FIG. 13 (b) to the corresponding NB concentration. It can be seen that the luminescence intensity of the sample decreases exponentially with increasing NB concentration in the range of 0-500ppm NB concentration, satisfying the functional relationship y =777.9exp (-x/8.3) +1064.2exp (-x/118.9) +158.8, with a degree of fit R 2 =0.9990; has good linearity in the range of NB concentration of 0-10ppm, satisfies y =1962.9-63.9x, and has linearity of R 2 =0.9859. Combining the slope and the detection limit calculation formula, the detection limit of the Eu-MOFs sample on NB is calculated to be about 1.653ppm, and the detection limit is lower than most reports in the literature. The prepared Eu-MOFs has excellent detection limit on NB. Based on equation (3), the results of Stern-Volmer analysis of Eu-MOFs for NB quenching are shown in FIG. 13 (d). The NB concentration is in the range of 0-500ppm, the Stern-Volmer curve of NB satisfies the linear relation y =1.1+0.02x, and the linearity R 2 =0.9923, and the quenching constant K of Eu-MOF for NB was calculated SV ＝0.048ppm -1 . These results indicate that Eu-MOFs has good sensitivity to NB, which can be detected by luminescence quenching method.
Example 5:
a hollow rare earth-based MOFs material based on a solvothermal method is characterized in that the preparation method comprises the following steps:
1mmol (0.210 g) of H is weighed 3 BTC and 1mmol (0.172 g) of H 2 Powder of TDC, and Tb (NO) 3 ) 3 ·6H 2 O and Eu (NO) 3 ) 3 ·6H 2 O powder, retaining Tb 3+ And Eu 3+ The total amount of substances is 1mmol 3+ The amounts of substances of (a) are x =0,0.02,0.04,0.06,1mmol, tb, respectively 3+ The amount of the components is 1-x respectively, preparing Tb in different proportions 3+ /Eu 3+ Ln-MOFs materials
Mixing the three solutions prepared in the step 1), and heating the mixture in a closed system for reaction; the reaction temperature range is 150 ℃, and the reaction time is 72h.
And 3, carrying out solid-liquid separation on the product after the reaction, and washing the obtained solid product by adopting DMF (dimethyl formamide) to obtain the hollow rare earth-based MOFs material.
Experimental part:
PXRD results of the prepared Ln-MOFs powder samples are shown in FIG. 2 (a), and the results show that the positions of diffraction peaks of the Ln-MOFs samples are basically the same, and the structures of the Ln-MOFs samples have better consistency. The Thermogravimetric (TG) curve of the Ln-MOFs powder sample is shown in figure 2 (b), the Ln-MOFs sample obviously loses weight at 135-326 ℃ for the first time, the stage is a continuous weight loss stage, the weight loss is about 14 percent, the boiling point of DMF is 152.8 ℃, and the weight loss at the stage is mainly caused by DMF volatilization; the other obvious weight loss range is 526-620 ℃, which is mainly due to the collapse of a sample framework, the weight of the sample is rapidly reduced to about 622 ℃ and the decomposition is complete, and the weight loss is about 31%. Therefore, the prepared Ln-MOFs has a stable space structure below 526 ℃.
The shape analysis result of a Scanning Electron Microscope (SEM) shows that the prepared Ln-MOFs is a hollow spherical Ln-MOFs formed by orderly and alternately stacking nano-scale small crystal particles. The specific formation process of hollow spherical Ln-MOFs is shown in fig. 3 (a) and (b), and mainly includes the following two stages: (a) In the early stage of growth, the organic ligand is reacted with Ln 3+ Self-assembled alignment reaction is carried out to generate Ln-MOF nano blocks; (b) The nano-blocks are orderly staggered and stacked for self-assembly to form hollow spherical Ln-MOFs (FIG. 3).
Comparing with and without H 2 The morphology of Tb-MOFs formed by TDC (FIGS. 4 (a), (b)) found that no H was added 2 Tb-MOF of TDC is self-bundled into stable rod bundle by one nanorod without forming a hollow structure, and H is added 2 Tb-MOF of TDC forms a hollow sphere structure formed by staggered stacking of nano blocks, and the staggered stacking of the hollow sphere structure makes the hollow sphere structure more stable, wherein the hollow sphere structure can not be formed in ultrasonic treatment for 20minDestroyed and more porous than the normal MOFs, facilitating a variety of applications. The successful synthesis of the hollow spherical Ln-MOFs provides a new preparation method for the preparation of hollow MOFs materials, and compared with the conventional hollow MOFs synthesis method, the method has the advantages of simpler operation, mild conditions, high yield, uniform product appearance, good stability, hopeful large-scale production and the like. Further, TEM and Mapping analysis (FIG. 4 (C-g)) of Tb-MOFs was carried out, and the results showed that the Tb-MOFs contained C, O, N and Tb elements and the single crystal analysis were identical, and that the result of Mapping of Tb element showed a shading of the sphere center, indicating that it was a hollow sphere, and the result of a line graph of Tb element distribution (FIG. 4 (h)) showed a depression in the middle of the sphere, indicating that the sphere center had an element deletion, further confirming the hollow sphere structure.
Containing H 2 Different TDC Tb 3+ 、Eu 3+ The morphology of the formulated Ln-MOFs is shown in FIG. 5, and the results show that different Tb' s 3+ 、Eu 3+ The hollow sphere structure of Ln-MOFs is not changed in the proportion, and the diameter of the hollow sphere is slightly changed (3-10 μm). Directly mixing Tb for determining whether the preparation process is harsh 3+ 、H 3 BTC、H 2 TDC and DMF to prepare Tb-MOF, whose morphology is shown in FIG. 5 (f), compared to FIG. 5 (a), direct mixing only reduced the diameter of the nanoblock from 7-8 μm to 4-5 μm, where the structure of the hollow sphere was not changed, indicating that this method does not require harsh preparation conditions. Further on H with different ratios 2 SEM test of Tb-MOF of TDC, as shown in FIG. 7, found that H was added in different ratios 2 The TDC does not change the appearance of the hollow sphere, and is a spherical structure formed by cross-stacking of nano blocks. Description of the use of H 2 TDC serving as a reaction auxiliary agent for preparing the hollow spherical Tb-MOF is not influenced by the addition amount, and further shows that the method has universality and does not need harsh conditions.
The synthesized bimetallic Ln-MOFs material can realize color conversion from green light to red light, and FIG. 7 (a) shows a fixed excitation wavelength E x =320nm, different H 3 BTC、H 2 And the emission spectrum of Tb-MOFs prepared under the condition of TDC proportion. In the figure, tb-MOFs have four emission peaks respectively positioned at 488nm,545nm,584nm and 621nmCorresponds to Tb 3+ Is/are as follows 5 D 4 → 7 F 6 ， 5 D 4 → 7 F 5 ， 5 D 4 → 7 F 4 And 5 D 4 → 7 F 3 and (4) transition. When H is present 3 BTC and H 2 When the TDC ratio is 1 1-x /Eu x -MOF (x =0,0.02,0.04,0.06, 1). FIG. 7 (b) shows the excitation wavelength E x ＝320nm，Tb 1-x /Eu x Emission spectrum of MOF (x =0,0.02,0.04,0.06, 1). Tb 1-x /Eu x MOFs shows Tb 3+ And Eu 3+ Characteristic emission of Tb 3+ The characteristic emission peak is consistent with that of FIG. 7 (a), and three emission peaks of Eu-MOFs are respectively located at 580nm,595nm and 617nm, and respectively correspond to europium ions 5 D 0 → 7 F 0 ， 5 D 0 → 7 F 1 And 5 D 0 → 7 F 2 and (4) transition. Observed and compared to find that the Tb is related to 1-x /Eu x Eu of the MOFs 3+ Increase in content, tb 3+ The intensity of the strongest emission peak at 545nm gradually decreases, and Eu 3+ The intensity of the strongest emission peak 617nm gradually increased. For Tb in FIG. 7 (b) 1-x /Eu x The color coordinate values of the emission of MOF (x =0,0.02,0.04,0.06, 1) were calculated to obtain the CIE color coordinate diagram (fig. 8 (a)), which is an image of the emission of each material under 365nm ultraviolet lamp. In fig. 8 (a), the color coordinates from position 1 to position 5 are (0.381, 0.445), (0.443, 0.393), (0.511, 0.343), (0.532, 0.330), (0.589, 0.317), respectively, and the luminescent color shows the course of green → yellow → orange → red-orange → red. Illustrating that Tb can be adjusted 3+ And Eu 3+ Tb is adjusted by the proportion of 1-x /Eu x -the luminescent color of the MOF. Tb-MOF and Eu-MOF emit stronger green light and red light respectively.
Bimetallic Ln-MOFs material having Tb 3+ And Eu 3+ Characteristic emission peak of the ion. By adjusting Eu 3+ /Tb 3+ Ratio of the components can be adjustedThe emission wavelengths of Ln-MOFs are combined to obtain different colors of luminescence, and the organic linking agent H is also illustrated 3 BTC、H 2 The TDC has a good antenna effect. To confirm Tb 3+ With Eu 3+ The excited states of Ln-MOFs are monitored at 545nm and 617nm respectively 5 D 4 (Tb 3+ ) And 5 D 0 (Eu 3+ ) The lifetime of (2) is as shown in FIG. 8 (b). Excited states of all bimetallic Ln-MOFs 5 D 4 (Tb 3+ ) Have shorter life than Tb-MOFs 5 D 0 (Eu 3+ ) The lifetime is longer than that of Eu-MOFs (see FIG. 8 (c)). Indicating the presence of Tb 3+ To Eu 3+ The energy transfer, the efficiency of energy conversion between donor and acceptor (E) can be calculated by the following formula:
E＝1-τ da /τ d
in the above formula, τ da Indicates the excited state lifetime in the presence of the acceptor, tau d Represents the excited state lifetime in the absence of acceptor, calculated as Tb 1-x /Eu x The energy conversion efficiency of MOF (x =0.02,0.04, 0.06) was 18%,19% and 28%, respectively. The quantum yield test results of Ln-MOFs are shown in Table 6, and the quantum yields of the bimetallic Ln-MOFs are lower than that of Tb-MOF and higher than that of Eu-MOF.
TABLE 6 Tb 1-x /Eu x Quantum yield of MOF (x =0,0.02,0.04,0.06, 1)
Claims (10)
1. A preparation method of a hollow rare earth-based MOFs material based on a solvothermal method is characterized by comprising the following steps of:
1, mixing lanthanide metal salt and 1,3, 5-benzenetricarboxylic acid H 3 BTC and thiophene-2, 5-dicarboxylic acid H 2 Respectively placing the TDC in a reactor, and adding a solvent for dissolving;
mixing the three solutions prepared in the step 1), and heating the mixture in a closed system for reaction;
and 3, carrying out solid-liquid separation on the product after the reaction, and washing the obtained solid product to obtain the hollow rare earth-based MOFs material.
2. The preparation method of the hollow rare earth-based MOFs material based on the solvothermal method, according to claim 1, wherein the preparation method comprises the following steps: in step 1, the lanthanide metal is trivalent rare earth metal, and the acid radical is an acid radical capable of dissolving rare earth ions.
3. The method for preparing hollow rare-earth-based MOFs materials based on the solvothermal method according to claim 2, wherein: in the step 1), the lanthanide metal is terbium, europium, praseodymium, samarium or cerium, and the acid radical is nitrate radical, acetate radical, sulfate radical or hydrochloride radical.
4. The preparation method of the hollow rare earth-based MOFs material based on the solvothermal method, according to claim 1, wherein the preparation method comprises the following steps: in step 1), the metal salt is selected from soluble rare earth salts and mixtures thereof.
5. The method for preparing hollow rare-earth-based MOFs materials based on the solvothermal method according to claim 1 or 2, wherein: in the step 1, the solvent is N, N-dimethylformamide DMF of AR level.
6. The method for preparing hollow rare-earth-based MOFs materials based on the solvothermal method according to claim 5, wherein: in the step 2, heating the mixture in a high-pressure reaction kettle for reaction.
7. The method for preparing hollow rare-earth-based MOFs materials based on the solvothermal method according to claim 5, wherein: in the step 3, separating by using a centrifuge tube, and carrying out centrifugal washing by using DMF (dimethyl formamide); after washing, the product obtained is dried.
8. Hollow rare-earth-based MOFs material according to claim 5 based on solvothermal methodThe preparation method is characterized by comprising the following steps: h 3 BTC and DMF participate in lanthanide metal cation coordination; h 2 TDC is taken as a reaction auxiliary agent and is not coordinated with lanthanide metal cations; eventually a hollow sphere structure centered on the lanthanide metal cation is formed.
9. The method for preparing hollow rare-earth-based MOFs materials based on the solvothermal method according to claim 8, wherein: in the step 2, metal salt formed by two lanthanide metals is adopted to finally obtain the hollow bimetal MOFs material.
10. The method for preparing hollow rare-earth-based MOFs materials based on the solvothermal method according to claim 9, wherein: the two metals have different characteristic emission peaks, and the emission wavelength of the MOFs is adjusted by adjusting the proportion of the two metals.
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