LU503611B1 - An organic samarium metal framework material, its production process and application - Google Patents

Abstract

The present invention discloses an organic samarium metal framework material, the production method and application thereof, which belongs to the technical field of metal organic framework materials, the organic samarium metal framework material is prepared by a hydrothermal process using samarium nitrate as a metal source and 6-(4'-carboxyphenyl)pyridic acid synthesized as a ligand together with 4,4'-bipyridine, N,N-dimethylformamide, water and HNO3. The organic samarium metal framework material was used as a multifunctional fluorescent probe for the highly sensitive detection and identification of the 3+ − 10 metal ion Bi and the inorganic anion MnO4, and thus a 3+ − fluorescence sensor system was developed for the detection of Bi and MnO4 in aqueous solution, 3 + − the linear ranges were 20-90 µM (Bi ) and 0-100 µM (MnO4), the detection limits 3+ − were 1.06 µM (Bi ) and 4.59 µM (MnO4), respectively. This organic samarium metal framework was used for the detection of Bi3+ in real water samples with recoveries in the range of 15 98.00-102.00% and relative standard deviations in the range of 1.54-3.35%.

Description

An organic samarium metal framework material, its production process and-V503611

Application

Technical part

The present invention relates to the technical field of organometallic

Framework materials, in particular an organic samarium metal framework material

Manufacturing process and application.

Technology in the background

The rapid development of industry has led to more and more pollutants being released into the

environment are released, which have numerous negative effects on human beings

have health and life. Conventional detection methods such as mass spectrometry,

Atomic emission spectrometry and liquid chromatography require sophisticated and expensive

Instruments and mastery of how they work. In comparison, this applies

Luminescence sensing as a promising detection method because it is easy to use, responds quickly and has low detection limits. Bismuth and its compounds have been used extensively as a metal additive and for the recovery of uranium nuclear fuel.

Contamination of water by bismuth leaks can cause various health problems in humans

Diseases such as kidney disease, stomatitis, bone and joint disease and colitis. Therefore, the rapid detection of bismuth ions in water is of great importance for human health. The permanganate ion is not only very soluble in water, but also an important oxidizing agent, excessive amounts of MnO4 ions can cause certain

have an impact on human health, e.g. B. Gastrointestinal disorders, liver and

Kidney damage and deformities. If the water contains large amounts of MnO4 ions, it can cause skin irritation and have a negative effect on the respiratory system. Therefore, it is necessary to develop a highly sensitive and selective chemical sensor for the detection of

To develop bismuth and permanganate ions for ecological, pharmaceutical and industrial purposes.

Metal-organic frameworks (MOFs) are one-, two-, or three-dimensional extended structures formed by the self-assembly of organic ligands with multiple binding sites in the form of ligand bonds to metal ions or

Metal clusters are formed, with unique pore topologies, high specificity

Surfaces and the availability of functions within the pores and external

Surface modifications that enable them for gas storage/separation, diversification of

Drugs that make catalysis, proton conduction, sensing, etc. potentially useful.

Luminescent MOFs have made great progress in synthesis in recent years

design and sensing applications and have attracted the attention of many researchers as an ideal sensing material. In particular, organometallic lanthanides

Skeletal materials have unique advantages in selective due to their combination of n-conjugation of organic ligands and luminescent properties of lanthanide ions

Detection and detection of metal cations and inorganic anions and were in the

areas of environmental science, medicine, life sciences and the nuclear industry. The most commonly reported cation sensors include Fe**, Al', Cu?*, Zn?" etc., while the most commonly reported anion sensors are Cr207", CrO4", F~ etc. However, we do not have any report of the detection of Bi°* through organic lanthanide

Metal skeletons have been found, and there are only three reports of the detection of Bi°* by organic transition metal skeletons: one by Wang et al. synthesized Cu-MOF became the

Detection of Bi** ions was used, and the detection limit could reach 4.3x10® mol/L203611

Gao et al. successfully constructed an AI-MOF for the detection of Bi** ions in aqueous

Solutions with a detection limit of 2.16x10° mol/L. El-Sewify et al. successfully modified the water-insoluble organic probe rhodamine-ethylenediamine-salicylaldehyde (RES) directly on Zr-MOFs to produce ultramicroporous fluorescent chemosensors (SFCs).

Detection of Bi** ions in aqueous solutions with a detection limit of 10” mol/L.

The luminescence mechanism of MOFs includes electron transfer and

Energy transfer processes, such as charge transfer from metal ions to organic ligands (MLCT), charge transfer from ligands to metals (LMCT), charge transfer from

Ligand to ligand (LLCT) and metal to metal charge transfer (MMCT), etc.

Thus, luminescent metal-organic framework materials have a rich and diverse spectrum of luminescence mechanisms. In contrast, there was in the state of

Technically no relevant research work on metal-organic samarium framework materials for luminescence.

Content of the invention

In response to the above problems, the present invention aims to provide an organic samarium metal framework, its production method and application, which is synthesized by a hydrothermal method using samarium nitrate as a metal source and 6-(4'-carboxyphenyl)pyridic acid as a ligand as a multifunctional fluorescent probe for the highly sensitive sensor detection of metal ions

Bi*” and inorganic anions MnO4 can be used.

In order to achieve the above objectives, the following technical solutions are used in the present invention:

A method for producing organic samarium metal framework material, characterized in that it comprises the following steps,

S1: The samarium metal source, the ligand, 4,4'-bipyridine, N,N-dimethylformamide, water and HNO; were placed in a hydrothermal reaction kettle, heated to 150-180°C at atmospheric pressure and kept at a constant temperature for 60-84 hours;

S2: Lowering the temperature of the hydrothermal reaction vessel to 30 ° C and removing the mixture from the reaction vessel;

S3: The mixture obtained in step S2 is washed with water or ethanol, filtered and dried to obtain a yellowish chunky complex, which is the organic samarium metal framework.

Furthermore, the samarium metal source described in step S1 is Sm(NO3)3.6H20 and the

Ligand is 6-(4'-carboxyphenyl)pyridic acid.

Furthermore, the molar ratio of Sm(NO3)3.6H20, 6-(4'-carboxyphenyl)pyridic acid and 4,4'-bipyridine in step S1 is 1:1:1 and the volume of N,N-dimethylformamide and water is 1: 4.

Further, in step S1, the hydrothermal reaction vessel is heated to 160° C. at atmospheric pressure and is maintained at a constant temperature for 72 hours.

Furthermore, in step S2, the temperature of the hydrothermal reaction vessel is set at a

Speed reduced from 4°C/h to 30°C.

Furthermore, the organic samarium metal framework material is as described above

Process manufactured.

Furthermore, the use of the organic samarium metal framework material in the detection before 503611

Water samples.

Furthermore, the organic samarium metal framework material is used for the detection of Bi** and

MnO4 used in water samples.

The advantageous effects of the present invention are: 1. The organic samarium metal framework material used in the present invention

samarium nitrate as a metal source and 6-(4'-carboxyphenyl)pyridinic acid as a ligand, which were treated with 4,4'-bipyridine, N,N-dimethylformamide, water and HNO; is synthesized by a hydrothermal process with a simple synthesis process and easy handling. 2. The organic samarium metal framework material of the present invention was designed as a multifunctional fluorescent probe for the highly sensitive detection and identification of the

Metal ion Bi°” and the inorganic anion MnO4 were used, and so a

Fluorescence sensor system developed for the detection of Bi** and MnOs™ in aqueous solution, the linear ranges were 20-90 uM (Bi**) and 0-100 uM (MnOy”), the detection limits were 1.06 uM (Bi) and 4.59 µM (MnO«”). This organic samarium metal framework material was used for the detection of Bi** in real water samples with recoveries in the range of 98.00-102.00% and relative standard deviations in the range of 1.54-3.35%, the high detection efficiency and accuracy of the organic synthesized in the present invention Samarium metal framework material confirms the feasibility and accuracy of the

Proof of Bi?” in real water samples, and its diverse sensing properties may lead to its further development as a potentially valuable material for the optical detection of

lead to environmental pollutants.

Description of the accompanying drawings

Figure 1 shows the results of X-ray single crystal analysis of Sm-MOF crystals in the present invention.

Figure 2 shows the powder diffraction pattern of Sm-MOF in the present invention.

Figure 3 shows a TGA diagram of the Sm-MOF in the present invention.

Figure 4 shows SEM images of the Sm-MOF crystals and the powder in the present

Invention.

Figure 5 shows the infrared spectrum of Sm-MOF in the present invention.

Figure 6 shows the fluorescence spectra of Sm-MOF in different solvents in the present invention.

Figure 7 shows the emission spectra of Sm-MOF in aqueous solution at different

Excitation wavelengths in the present invention.

Figure 8 shows the fluorescence spectra of Sm-MOF in different metal ion solutions in the present invention.

Figure 9 shows the effect of different pH values on the sensing of Bi** by Sm-

MOF in the present invention.

Figure 10 shows the luminescence spectra and linear relationship of Sm-MOF at different concentrations of Bi** in aqueous solution in the present invention.

Figure 11 shows the fluorescence intensity of Sm-MOF in 13 anion solutions in the present invention.

Figure 12 shows the effects of different pH values on the sampling of MnO4

Sm-MOF in the present invention.

Figure 13 shows the luminescence spectra and linear relationship of Sm-MOF in different concentrations of MnO4” in the present invention. LU503611

Figure 14 shows the UV spectra of Sm-MOF in the present invention immersed in various anionic aqueous solutions.

Figure 15 shows the fluorescence lifetime diagrams for Sm-MOF and Sm-MOF+ MnO47 aqueous solutions in the present invention.

Figure 16 shows the results of the selective detection of Bi°* by Sm-MOF in

Presence of interfering ions in the present invention.

Detailed description

For a better understanding of the technical solution of the invention for a person skilled in the art, the technical solution of the invention is attached below in connection with the

Drawings and embodiments described in more detail.

Embodiment 1:

Reagents and devices used in the present invention include:

Main reagents: Sm(NO3);:6H20, 6-(4'-carboxyphenyl)pyridic acid (H2CPA), 4,4-

Bipyridine, N,N-dimethylformamide (DMF), HNO; (10%), NaOH (0.1 mol/L), the reagents used for synthesis and scanning are analytically pure without further purification, that

Water is ultrapure water.

Main instruments: Elementar Vario II elemental analyzer (Elementar, Germany); UV-3600 Ultraviolet Spectrophotometer (Shimadzu, Japan), ZPY-2P Thermogravimetric

Analyzer (Shanghai Kaiping Instrument General Factory); IRAFFINITY-1S optical Fourier

Transform infrared spectrometer (Shimadzu, Japan); D8 advance X-ray powder diffractometer (Bruker GmbH, Germany); F-7000 Fluorescence Photometer (Shimadzu, Japan), TM3000

scanning electron microscope (Hitachi, Japan); Bruker APEX-II CCD single crystal diffractometer (Bruker GmbH, Germany).

A method for producing organic samarium metal framework material, in particular comprising the following steps,

S1: The samarium metal source, the ligand, 4,4'-bipyridine, N,N-dimethylformamide, water and HNO; were placed in a hydrothermal reaction kettle, heated to 150-180°C at atmospheric pressure and kept at a constant temperature for 60-84 hours;

In particular, the samarium metal source is Sm(NO3)3-6H20 and the ligand 6-(4'-

Carboxyphenyl)pyridic acid (H2CPA). Sm(NO3)3-6H20(0.075 mmol), H2CPA (0.075 mmol), 4,4'-

Bipyridine (0.075 mmol), DMF (1 mL), H2O (4 mL) and 10% HNO; (3 drops) were added to 25 mL of a PTFE hydrothermal reaction kettle, then the temperature was reduced for 72

hours at atmospheric pressure increased to 160°C.

S2: The temperature of the hydrothermal reaction kettle is reduced to 30°C at a rate of 4°C/h and the mixture in the hydrothermal reaction kettle is removed;

S3: The mixture obtained in step S2 is washed with water or ethanol, filtered and dried to obtain a yellowish lumpy complex, which is the organic samarium metal framework Sm-MOF (48% yield based on Sm).

Furthermore, the organic samarium metal framework Sm-MOF, which was prepared by the method described above, was tested and subjected to luminescence sensing experiments.

The test method is specified as follows:

Crystals with good crystallinity and suitable size (Sm-MOF crystals) were selected and placed in a Bruker APEX-II CCD single crystal diffractometer for single crystal testing

(equipped with an Oxford Cryostream 800 cryogenic unit), and dt&}503611

X-ray diffraction data were collected at 296.15K with a Mo Ka radiation source (A = 0.71073 A). Data recovery is carried out using the SAINT procedure. For all

The SADABS multi-scan methods were used for absorption corrections. The resolution 5 of the structure is obtained using both the SHELXT and XL methods via F2 full matrix

Least squares optimized for two methods of refined optimization. The non-

Hydrogen atoms are refined by anisotropic temperature coefficients. The

Hydrogen atoms are all determined by theoretical hydrogenation. The

PLATON/SQUEEZE process was used to remove disordered solvent molecules from the structure. The crystallographic data for the complexes are shown in Table 1 and the main bond lengths and angles are shown in Table 2.

Table 1 Sm-MOF crystallographic data

Complex Sm DICH VolumetÀ 33 ERG)

Empirical formula CecHasNy sax | X1

Formula weight 1098.38 Peale gens’ A086

Temperature (KX) 398.15 to 343$

Wavelength <A} 2.71073 EOE 3382

Kristalisystem space group Triklin “PS Theia area for data acquisition ©} 54846 55.454 a’ 4 SS Collected reflections S40 wA 186803433 Independent reflections 3815 Re 5143 Kulm. 0286}

A 14.056000 Data/restrictions parameters IPFA ai 1625713 Adjustment tolerance for F2 1925 ges 4.326448} Final R-indices {F>2 sigma(1)] Boe DER why = DATIS 3 161.955 R-indices (all data} Ry > QDIRE wily » 46727

Table 2 Partial bond lengths (A) and bond angles (°)

Bond lengths A bond lengths À bond lengths À bond lengths A

Saat 0 TALE Bela 24352) Seat-035 28379) Si-O 251088 3-05 329TH Srl Lise LIEGE SmI DAI Sm 1-08 RRC

Bond angle x bond angle. Bond angle + bond angle.

QE-Smi-Q2a BASED) ObSni-0in 14498083 OLSmiOSr TISNEIO OSeSmi08 TRIE

O1Sml03 SISHE CHbSmiCHE SIAN ORBmLOT TRAMIN OlSmiOf TRAN:

Cib-Smi-05 FLIX) ORSmiD8 HET) OFSmiOIz IICIKIO Obama? LAAIIM

OT-Emt-03h 8488016) OLSml.O8 746383 C6oSml-D1 3470081 OTAmi.O TIENIS

OS-Smi-Qt 788001 Met Qi 7184080) OTEml.08 MSI) OlsSmtORE IN

Oi-Rrat-0la TREND OSeBmi-O8d SISIGS 7 Ols-Si-0S TE720) © OS-Sa Ob 1342600)

Oéc-Srst lb I2SHRS) OGRal-O8h L1M40H9} OSSmiQib SII) OScAmbO? SEGA

Symmetry Conversions to Generate Equivalent Atoms: a-x~y bbl by 2g O- 17x 552

The specific procedure for the luminescence sensor experiment is: 3 mg of Sm-MOF powder was dissolved in 3 mL of M(NO3}) or KyX solution with a solubility of 10?mol-L! or 3 mL of aqueous solution with different concentrations of Bi?” (or

MnOy”) immersed. Where M=Pb"", Sr**, Ag", Bi", Zn", Co", Mg", Ni?*, K*, Na", Cu?" or

Fe’, DI&S03611

Suspension was sonicated for 30 minutes and before measuring the fluorescence intensity 2

Left at room temperature for days.

The results of the tests and luminescence experiments include: 1. Crystal structure

The results of the X-ray single crystal analysis are shown in the attached Figure 1, in the attached Figure 1, a is the asymmetric F unit diagram of Sm; b is that

Coordination diagram of the ligand; c is the coordination diagram of the metal and the binary metal unit, the one-dimensional link and the two-dimensional surface; d is the three-dimensional structure of Sm-MOF; As can be seen in the accompanying Figure 1, the asymmetric unit of the complex consists of a crystalline independent Sm ion, a

Semiligands and two ligated water molecules (as shown in the attached Figure 1).

The ligands have two coordination modes: **:**+#3 which is bound to three Sm ions, and X:s:X:#$ which is bound to four Sm ions (as shown b in the accompanying Figure 1) .

The metal Sm ion forms an 8-ligand pattern with six oxygen atoms from five ligands (01, O2a, OS, O6a, O3b, O4b) and two oxygen atoms from two water molecules (07, O8) (as c in the accompanying Figure 1 ). The two Sm ions are connected via two pairs of oxygen atoms (O1, O2 and Ola, O2a) to form a binary metal unit, which is linked via a ligand to form a one-dimensional chain, with the link being connected to the link via the

Ligands form a two-dimensional surface (like c in the attached Figure 1). The surfaces are connected to each other by ligands and form a three-dimensional pore-like structure (as in the attached figure 1). 2. Structural characterization 2.1 PXRD and TG analysis

The positions of the diffraction peaks of the PXRD test results for Sm-MOF are consistent with those of the simulated diffraction peaks, as shown in the accompanying Figure 2, indicating that the complexes have good phase purity. To the thermal

To determine stability of the complexes, the TG curves of the complexes were tested in the range of 30-800°C (at a rate of 10°Cemin™') and the results are shown in the attached Figure 3, from which it can be seen that there were two weight losses during the

There is a heating process, the first between 160-220°C should be the loss of ligand water with a weight loss of 6.7% (theoretical value of 6.6%), the second time between 470-570°C, which can be attributed to the collapse of the entire skeleton , and after 570°C it's basically a plateau. The complex is therefore relatively stable up to 470°C. 2.2 SEM, elemental and infrared analysis

The attached Figure 4 shows scanning electron micrographs of Sm-MOF

Crystals and powder shown, in the attached Figure 4 a is a scanning electron micrograph of Sm-MOF crystals and b is a scanning electron micrograph of Sm-MOF powder. As shown in the accompanying Figure 4, the grains of Sm-MOF have a good hexagonal structure, and the scanning electron micrograph (SEM) image of the powder shows some irregular defects, indicating that the material contains some voids.

Elemental analysis of Sm-MOF gave (%): C, 41.95; H, 2.72; N, 23.98. Theoretical

Values (%): C, 42.71; H, 2.65; N, 23.36.

The infrared spectrum of Sm-MOF is shown in the accompanying Figure 5, with a 1/503611 broad characteristic absorption peak at 3378cm™, which belongs to the -OH stretching vibration in the coordinated water molecule, suggesting that Sm is connected to the hydroxyl group in the

Water molecule is coordinated as O-H, and two characteristic absorption peaks of

Carbonyl are at 1657cm™, 1514cm™, 1419cm”', which are symmetrical vs(coo” and asymmetrical vas(coo” stretching respectively, by calculating the AY &="'s! Difference value of the compound it can be concluded that the carboxylic acid -Coordination mode with the metal ion-

Coordination mode is connected. 3. Fluorescent properties of the complexes 3.1 Influence of the solvent on the fluorescence intensity of the complexes

The Sm-MOFs were dispersed in different solvents according to the experimental sensing method, the results are shown in the attached Figure 6, the

Difference between fluorescence intensity in aqueous solution and in others

Solvents are not significant considering the non-toxicity and stability of the aqueous ones

Solution in mind, so that water acts as a solvent for the capture substances in this

Invention is chosen. The fluorescence spectra at different excitation wavelengths were also examined, and the results are shown in the accompanying Figure 7, it can be seen that the emission peak is most obvious at an excitation wavelength of 300 nm, which is why 300 nm was chosen as the excitation wavelength for detection. 3.2 Metal cation sensing experiments

The sensing results of the complex for various metal ions are provided in the attached

Figure 8 shows the luminescence intensity after immersing the complex in aqueous

Solutions containing Bi?* increased significantly (approximately 6-fold), while it hardly changed for the other metal ions, indicating that the complex has a high

Selectivity for the fluorescence detection of Bi°”.

In order to find the best sensor medium, the present invention also included the

The effect of different pH buffer solutions on the sensor sensitivity was investigated, and the

Results are shown in the attached Figure 9 (pH=1 is 0.1 mol/L HCl solution, 1<pH<7 is HAC-NaAc buffer solution, 12>pH>7 is NH3-H2O-NH4Cl buffer solution and pH is 12 0.01

NaOH solution). It can be seen that the difference between the fluorescence intensity I of

Sensor system and the fluorescence intensity Io of the blind system is greatest if none

Buffer solution is added, so no buffer medium was added in this experiment.

With the increase of the Bi*" concentration (from O to 190 yumoleL") the

Fluorescence intensity of the system gradually increases, as shown in the accompanying Figure 10, and the

Luminescence intensity of the system showed a good linear relationship with Bi** concentration when the Bi** concentration was between 20-90 µmoleL": y=75.92x-234.88 (R?=0.9974), as shown in the attached Figure 10 and the detection limit calculated from 3o/f was 1.06x10°mol/L (where 6 is the standard deviation of the fluorescence intensity of 11-fold

blank samples and k is the slope of the linear relationship). This Sm-MOF fluorescent sensor offers higher sensitivity and better selectivity for detecting Bi*” than that

State of the art. The sensitization effect of the Bi**-Sm-MOF system could be on the

heavy atom effect of Bi°*, which leads to an improved scramble efficiency between the systems from the singlet state S1 to the triplet state T1. The addition of

Bi** can lead to a better match between the x" orbitals of the ligand and déi/503611

Resonance energy levels of Sm** result in efficient energy transfer from the ligand

Sm** promotes and further sensitizes the antenna effect. 3.3 Experiments for scanning inorganic anions

The results of fluorescence detection in inorganic anions by the complexes are shown in the accompanying Figure 11, which shows that most of the anions

Fluorescence of Sm-MOF more or less destroy, but MnO4” is the most obvious, to understand the influence of the medium on the sensor sensitivity are the corresponding

Results for MnO4 sensing in various pH buffer solutions are shown in the attached Figure 12 (buffer medium pH=1 is a 0.1 mol/L HCI solution, 1<pH<7 is a HAC-NaAc solution.

Buffer solution, 12>pH>7 is a NH3-H2O-NH4Cl buffer solution and pH 12 is a 0.01 NaOH

Solution). It can be seen that the difference AF between the fluorescence intensity F of

Sensor system and the fluorescence intensity Fo of the empty system is greatest when none

Buffer solution is added, which is why this experiment was chosen without buffer medium.

With increasing MnOy concentration (from O to 800umolL!) the

Luminescence intensity of Sm-MOF significantly weaker, as shown in the attached Figure 13. When the MnO4 concentration was between 0-100 umoleL"!, there was a good linear relationship between the two: y=17.803x+4266.95 (R°=0.9929), as shown in the inset of the attached Figure 13, with a limit of detection of 4.59x10°mol/L ( 3k 6 denotes the standard deviation of the fluorescence intensity of the blank sample, k denotes the

Pitch).

To investigate the mechanism of the fluorescence burst of the complexes due to MnO4”, the UV spectra of Sm-MOF in the presence of various inorganic

ions recorded (see attached Figure 14), it was found that only MnO4 had one

Absorption peak in the range of 250-350 nm, while the other anions in this

Do not absorb wavelength range. In addition, the position of the

Absorption peaks almost with the excitation peak of Sm-MOF-, suggesting that a

Energy transfer between Sm-MOF and MnO4" takes place, so this could be the cause of the

Fluorescence burst of the complexes due to MnO4” can be attributed to the competition between MnO4 and Sm-MOF in the UV range for absorption. Furthermore, the

Fluorescence lifetimes of Sm-MOF in aqueous solution and Sm-MOF+MnO4 in aqueous solution

Solution measured, the results are shown in the attached Figure 15, and it can be found that the fluorescence lifetimes of both are almost the same, indicating that the fluorescence burst of Sm-MOF by MnO4” may be a static burst. 4. Measurement of experimental samples 4.1 Anti-interference experiments

The results of the anti-interference of the Sm-MOF complex against Bi*°° in the presence of other metal ions are shown in the accompanying Figure 16, which shows that the

Fluorescence intensity of the complex only decreases slightly in the presence of other metal ions.

In contrast, the fluorescence intensity is increased by the addition of Bi? immediately reinforced. The

Complexes have high selective recognition of Bi** in the presence of other metal ions. 4.2 Detection of Bi?” in water samples

The Yanhe water, the tap water and the mountain spring water were filtered, boiled and concentrated 100 times, and 1 mL of the water sample was taken for determination by ab/503611 experimental method while the spiking recovery test was carried out, the results are in the table below 3 listed. The results showed that the Bi** content in the water samples was between 0.002-0.004 umol-L" (according to concentration), which is consistent with the values reported in the literature [5] and [14].

Table 3 Applications for the detection of Bi** in real samples (n=8)

Sample Measured Values Sanguine Added Added Total Measured Value Total found Return Gain

Sample De RS Aumol/L3 AumoLL3 Recovery

Mountain spring water ©6023 3.35 5.0080 2.697289 39.38

Tap water 8.0020 3.58 QO050 2006987 9 94

Yanke water 0.0034 2.35 3.0050 {1.008308 gi 12 [S]Carballo S,Teran J,Soto R M,et al. Green approaches to determine metals in lubricating oils by electrothermal atomic absorption spectrometry (ETAAS)[J] Microchemical

Journal,2013,108(1):74-80.

[14] Bausinger T, Preuss J Stability of nitroaromatic specialty explosives in reversed-phase liquid chromatographic systems[J].Journal of Hazardous Materials,2009,162(2-3):1578-1582.

In summary, in the present invention, a three-dimensional Sm-MOF

Sensor material based on 6-(4'-carboxyphenyl)pyridinic acid (H2CPA) was successfully constructed, and fluorescence analysis revealed that the complex was multifunctional

Fluorescence probe for the highly sensitive scanning of metal ions Bi** and inorganic

Anions MnO4 was used, the recovery rates of Bi** in the current

Water samples ranged from 98.00%-102.00% with relative standard deviations of 1.54%-3.35%. The feasibility and accuracy of the complex for the detection of Bi** in real water samples has been demonstrated. The diverse sensor properties of Sm-MOF have led to its further development as a potentially valuable material for optical

Detect environmental pollutants.

The above statements show and describe the basic principles of the invention

Main features and advantages of the invention. It should be clear to the expert that the

Invention is not limited by the above embodiments that the above

Embodiments and the description in the description merely outline the principles of

Illustrate the invention and that there are various variations and improvements to the invention

Invention exists that fall within the scope of the invention claimed for protection without departing from the spirit and scope of the invention. The scope claimed for the present invention is defined by the appended claims and their equivalents.

Claims (8)

Claims LU503611 1. A method for producing samarium organic metal framework material, characterized in that it comprises the following steps, S1: The samarium metal source, the ligand, 4,4'-bipyridine, N,N-dimethylformamide, water and HNO; were placed in a hydrothermal reaction kettle, heated to 150-180°C at atmospheric pressure and kept at a constant temperature for 60-84 hours; S2: Lowering the temperature of the hydrothermal reaction vessel to 30 ° C and removing the mixture from the reaction vessel; S3: The mixture obtained in step S2 is washed with water or ethanol, filtered and dried to obtain a yellowish chunky complex, which is the organic samarium metal framework. 2. A method for producing organic samarium metal framework material according to claim 1, characterized in that the samarium metal source described in step S1 is Sm(NO3)3-6H20 and the ligand is 6-(4'-carboxyphenyl)pyridic acid. 3. A method for producing organic samarium metal framework material according to claim 2, characterized in that the molar ratio of Sm(NO3)3-6H20, 6-(4'-carboxyphenyl)pyridine acid and 4,4'-bipyridine in step S1 1:1:1 and the volume of N,N-dimethylformamide and water is 1:4. 4. A method for producing organic samarium metal framework material according to claim 3, characterized in that in step S1, the hydrothermal reaction vessel is heated to 160 ° C at atmospheric pressure and maintained at a constant temperature for 72 hours. 5. A method for producing organic samarium metal framework material according to claim 4, characterized in that in step S2 the temperature of the hydrothermal reaction vessel is reduced to 30°C at a rate of 4°C/h. 6. Organic samarium metal framework material, produced by the manufacturing process according to one of claims 1-5. 7. Organic samarium metal framework material for use in detecting water samples according to claim 6. 8. Use of an organic samarium metal framework material in the detection of water samples according to claim 7, characterized in that the organic samarium metal framework material for the detection of Bi? and MnOy is used in water samples.