CN114570334A - Preparation and application of water system stability MOFs/graphite phase carbon nitride composite material - Google Patents

Preparation and application of water system stability MOFs/graphite phase carbon nitride composite material Download PDF

Info

Publication number
CN114570334A
CN114570334A CN202210263346.5A CN202210263346A CN114570334A CN 114570334 A CN114570334 A CN 114570334A CN 202210263346 A CN202210263346 A CN 202210263346A CN 114570334 A CN114570334 A CN 114570334A
Authority
CN
China
Prior art keywords
mofs
composite material
water system
carbon nitride
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210263346.5A
Other languages
Chinese (zh)
Other versions
CN114570334B (en
Inventor
师彦平
康晶燕
赵晓博
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN202210263346.5A priority Critical patent/CN114570334B/en
Publication of CN114570334A publication Critical patent/CN114570334A/en
Application granted granted Critical
Publication of CN114570334B publication Critical patent/CN114570334B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a MOFs/g-C3N4The composite material is prepared by mixing MOFs material with g-C3N4The materials are calcined under the action of nitrogen flow after being mixed and ground; naturally cooling, dispersing in ethanol solution, ultrasonically treating, centrifuging to remove excessive graphite-phase carbon nitride material, and vacuum drying to obtain MOFs/g-C3N4A composite material. The graphite phase carbon nitride material is coated on the surface of the MOFs material layer by layer through electrostatic interaction in the thermal stripping process, and a thin film is formed on the surface of the MOFs material, so that water molecule pairs are effectively blocked from further approaching the center of a metal ion to provide an activation energy barrier to be overcome, and the MOFs material is effectively improvedThe hydrophobic property of the MOFs enhances the water system stability of the MOFs, effectively keeps the high-efficiency and high-selectivity adsorption performance of the MOFs material on different analytes, and can be used for selective extraction, enrichment, analysis and detection of different metal ions and vitamins in a complex matrix.

Description

Preparation and application of water system stability MOFs/graphite phase carbon nitride composite material
Technical Field
The invention relates to a MOFs/g-C3N4A preparation method of a composite material, in particular to a water system stability MOFs/g-C3N4A method for preparing the composite material; mainly used as solid phase extracting agent for metal ions in aqueous solution or acidic solution orThe high selectivity extraction and enrichment of organic micromolecules is used for realizing the sensitive detection of trace target analytes in complex matrix samples, and belongs to the field of composite materials and the technical field of analysis and detection.
Background
Since the 90 s of the 20 th century, the rapid development and application research of Metal Organic Frameworks (MOFs) has been attracting attention. As a porous crystalline material, MOFs has great application value in the aspects of absorption and separation of analytes, environmental monitoring, sensing detection, energy storage and the like due to the specific advantages of rich pore channel structures, ultra-high specific surface areas, diversity of design and combination of inorganic building units and organic ligands and the like. However, in the above-mentioned important applications of adsorption, separation and solid-phase extraction, the analyte to be detected inevitably exists in the aqueous environment, such as food, environmental water and even some acidic solutions, which puts higher requirements on the stability, adsorption selectivity and extraction capacity of the MOFs material in the aqueous solution or acid solution: (X.Z. Fang, Chem. Phys. Lett., 2021, 771, 138470;Y.Z. Zhang, ACS Appl. Mater. Interfaces, 2018, 10, 27868−27874). Therefore, the MOFs material with excellent water stability is developed, and the extraction performance of the MOFs material is regulated and controlled on the basis to meet the requirements of different application scenes, so that the method not only has important theoretical significance, but also has important practical significance for promoting the MOF to be the practical application of the material.
The water stability of the MOFs is mainly reflected by the strength of the interaction force between water molecules and the MOFs structure, and particularly shows the influence of the water molecules on the thermodynamic stability and the kinetic stability of the MOFs. The hydrolysis reaction of MOFs occurs mainly in two processes. First, the water molecules are close enough to the metal ion that the electron orbitals on the electrophilic metal ion interact with the nucleophilic water molecules. Second, the energy of the interaction must be large enough to overcome the activation energy barrier of the reaction and allow the hydrolysis reaction to occur. Therefore, the hydrophobicity of the framework structure of the MOFs plays an important role in improving the stability of the MOFs water system: (L.F. Yang, ACS Appl. Nano Mater., 2021, 4, 4346−4350, B.T. Liu, Environ. Sci.: Nano, 2020, 7, 1319–1347). In recent years, researchers have improved the water system stability of MOFs materials by improving the hydrophobicity of the framework structures of MOFs, such as by hydrophobizing organic ligand structures or modifying the hydrophilicity of the reserved metal cluster nodes with different functional groups (ii) (water system stability of MOFs materials)M.L. Ding, CCS Chem., 2020, 2, 2740–2748). However, these functionalization methods are developed for some specific MOFs materials, and have no general adaptation. Therefore, it is very important to develop a universal method capable of improving the stability of water systems of different types of MOFs.
Disclosure of Invention
The invention aims to provide a water system high-stability MOFs/g-C aiming at the current situation and the deficiency of research of MOFs materials in the field of separation analysis3N4The composite material can be used as a solid phase extracting agent for high-selectivity extraction and enrichment of metal ions or organic micromolecules in aqueous solution or acidic solution.
One, MOFs/g-C3N4Preparation of composite materials
The invention MOFs/g-C3N4The preparation of the composite material is that after the MOFs material and the graphite phase carbon nitride material are mixed and ground, the mixture is calcined under the action of nitrogen flow; naturally cooling, dispersing in ethanol solution, performing ultrasonic treatment for 20-30 min, centrifuging to remove excessive graphite-phase carbon nitride material, and vacuum drying to obtain MOFs/g-C3N4A composite material.
The MOFs material can be selected from ZIF series materials, MIL series materials and UiO series materials, and the mass ratio of the MOFs material to the graphite phase carbon nitride material is 100: 1-0.1: 1.
The grinding is carried out in an agate mortar, the graphite-phase carbon nitride material is uniformly wrapped on the surface of the MOFs material in the grinding process, the full contact between the functional groups on the surface of the MOFs and the amino functional groups on the surface of the graphite-phase carbon nitride material is facilitated, and the grinding time is 30-120 min.
The calcination temperature is 200-500 ℃, the heating rate is 1-5 ℃/min, preferably 2 ℃/min, and the calcination time is 120-480 min.
FIG. 1 shows MOFs materials, MOFs/g-C3N4And (3) a transmission electron microscope characterization image of the composite material. As can be seen in FIG. 1, the surfaces of the MOFs after high-temperature calcination are uniformly wrapped with g-C3N4Materials, show g-C3N4The amino functional group on the surface of the material and the MOFs surface group are subjected to electrostatic interaction in the secondary stripping process so as to be wrapped on the surface of the MOFs material, and the MOFs/g-C is prepared3N4A composite material.
II, MOFs/g-C3N4Aqueous stability of composite materials
The prepared MOFs/g-C3N4And (3) placing the material and the corresponding MOFs material in a nitric acid solution (0.5-5 mol/L) to measure the water system stability of the material. The results are shown in FIG. 2, unmodified g-C3N4The ZIF-67, the MIL-101 and the UIO-66 are dissolved and transparent in the strong acid solution, which is caused by the instability of MOFs materials in the strong acid solution and the collapse of the pore channel structure of the MOFs. Through g-C3N4MOFs/g-C after material wrapping3N4The material shows good stability in the same acid solution environment. This is due to the fact that under a nitrogen flow, g-C3N4The material is wrapped on the surface of the MOFs layer by layer through electrostatic interaction in the thermal stripping process, a thin film is formed on the surface of the MOFs material, and water molecule pairs are effectively blocked from further approaching to the center of a metal ion so as to provide an activation energy barrier to be overcome, so that the hydrophobicity of the MOFs material is effectively improved, the water system stability of the MOFs is enhanced, and meanwhile, the efficient and high-selectivity adsorption performance of the MOFs material to different analytes is effectively maintained. Therefore, the complex matrix can be used as a solid phase extraction agent for high-selectivity extraction and enrichment of metal ions or organic small molecules in an aqueous solution or an acidic solution so as to realize sensitive detection of trace target analytes in complex matrix samples, and belongs to the field of composite materials and the technical field of analysis and detection.
Drawings
FIG. 1 shows MOFs materials, MOFs/g-C3N4And (3) a transmission electron microscope characterization image of the composite material.
FIG. 2 shows MOFs materials and MOFs/g-C3N4Composite materials in aqueous and acidic solutionsStability test of (2).
FIG. 3 is ZIF-67/g-C3N4And (3) testing the selective extraction performance of the composite material on lanthanide.
FIG. 4 shows MIL-101/g-C3N4And testing the selective extraction performance of different vitamins.
FIG. 5 is UIO-66/g-C3N4And (3) testing the selective extraction performance of common divalent metal ions.
Detailed Description
The invention now provides the MOFs/g-C of the invention by means of specific examples3N4The preparation and properties of the composite material are further described.
Example 1
（1）ZIF-67/g-C3N4Preparation of composite materials
0.996 g of Co (NO) was weighed3)2·6H2Adding O solid powder into 100 mL of methanol solution, performing ultrasonic treatment to completely dissolve the O solid powder, weighing 1.312 g of 2-methylimidazole, adding the 2-methylimidazole into 50mL of methanol solution, stirring until the 2-methylimidazole is dissolved, gradually adding the 2-methylimidazole into cobalt nitrate methanol solution, and stirring at room temperature for 24 hours to obtain a ZIF-67 material;
weighing 5 g of melamine, placing the melamine in a 50mL porcelain crucible, placing the porcelain crucible in a muffle furnace, calcining the mixture at a high temperature for 4 hours at a heating rate of 4 ℃/min and at a temperature of 520 ℃, and cooling the mixture to room temperature after the reaction is finished to obtain graphite-phase carbon nitride (g-C)3N4) A material;
mixing ZIF-67 material with g-C3N4The materials are mixed according to the mass ratio of 100:1 and then are placed in an agate mortar for grinding for 30 min; the resulting mixed material was calcined in a tube furnace having a specification of 55X 25X 14 mm: the reaction temperature is 200 ℃, the heating rate is 1 ℃/min, the reaction time is 120min, and the whole calcining process is carried out in nitrogen flow. After the reaction is finished, placing the obtained product in an ethanol solution for ultrasonic treatment for 30min, then centrifuging to remove the redundant graphite-phase carbon nitride material, transferring the obtained product to filter paper, and drying in a vacuum drying oven (60 ℃), thus obtaining the ZIF-67/g-C3N4A composite material. Transmission electron microscope watch made of the composite materialSee figure 1 for characterization.
（2）ZIF-67/g-C3N4Stability testing in aqueous and acidic solutions
Accurately weighing the prepared ZIF-67/g-C3N450 mg of each of the material and the unmodified ZIF-67 material was placed in 5 mL of a nitric acid solution (0.5 mol/L), subjected to ultrasonic oscillation for 10min (power 4000W) in an ultrasonic wave, and then allowed to stand, and the results are shown in FIG. 2 (a). The results showed that the unmodified ZIF-67 material appeared purple transparent in acid solution, indicating that ZIF-67 was unstable in acid solution and the internal structure collapsed; and g-C3N4Material-wrapped ZIF-67/g-C3N4The material is characterized by g-C of the outer layer3N4The film forms an activation energy barrier which needs to be overcome, so that water molecules are effectively prevented from being close to metal ions, and the water system stability of the ZIF-67 is improved.
（3）ZIF-67/g-C3N4Performance of extracting and enriching lanthanide
Mixing 1.0 mg ZIF-67/g-C3N4Placing the composite material in 5 mL of lanthanide metal ion mixed solution (the concentration of each lanthanide metal ion is 20 mg/L), performing ultrasonic treatment for 10min to uniformly disperse the material in the solution to be detected, and then placing the mixed solution in an oscillator for 10min to achieve extraction balance; centrifuging at 4000 rpm for 20min to obtain separated adsorption material and water phase, measuring lanthanide concentration in mixed metal solution according to national standard, and calculating ZIF-67/g-C3N4Adsorption capacity of the composite material for lanthanide elements.
FIG. 3 is ZIF-67/g-C3N4The selective extraction performance of the composite material on lanthanide. The experimental results show that g-C3N4The selective adsorption performance of the ZIF-67 material is not influenced by the modification of the material, and the ZIF-67/g-C is in lanthanide solution3N4The material has good adsorption performance on ytterbium (Yb), and the adsorption capacity of the material is 2-7 times that of other metals, so that the material is ZIF-67/g-C3N4The method has high selective extraction and enrichment performance on ytterbium in lanthanide elements, and can be used for analytic determination of lanthanide metal ytterbium ions. Will be divided intoIsolated ZIF-67/g-C3N4Transferring the composite material into a centrifuge tube, adding 200 mu L nitric acid solution (0.5 mol/L), and performing 4000W ultrasonic treatment for 5 min to ensure that target metal ions are from ZIF-67/g-C3N4Desorbing on the composite material; repeating the above operations for 3 times, combining the desorption solution, and measuring the concentration of ytterbium (Yb) in the desorption solution by using an inductively coupled plasma emission spectrometer. The determination result shows that the content of target ion ytterbium in the eluent is 22.1 mg/L, namely 1 g ZIF-67/g-C3N4The composite material can selectively adsorb 13.06 mg of target ytterbium ions.
Example 2
（1）MIL-101/g-C3N4Preparation of composite materials
5.329 g of CrCl were weighed out3·6H2Adding 48 mL of deionized water into 3.32 g of terephthalic acid, stirring to uniformly mix, adding 1.25 mL of nitric acid (20 mmol), ultrasonically mixing uniformly, transferring to a high-temperature reaction kettle, heating in a 220 ℃ oven for 8 hours, naturally cooling, and centrifugally separating to obtain an MIL-101 material;
weighing 5 g of dicyandiamide, placing the dicyandiamide in a 50mL porcelain crucible, placing the porcelain crucible in a muffle furnace, calcining the porcelain crucible at a high temperature for 4 hours at a heating rate of 4 ℃/min and at a temperature of 520 ℃, and cooling the porcelain crucible to room temperature after the reaction is finished to obtain graphite-phase carbon nitride (g-C)3N4) A material;
mixing MIL-101 with g-C3N4The materials are mixed according to the mass ratio of 20:1 and then are placed in an agate mortar for grinding for 60 min; the obtained mixed material is placed in a tubular furnace with the specification of 120 multiplied by 60 multiplied by 18mm for calcination, the reaction temperature is 320 ℃, the heating rate is 2 ℃/min, the reaction time is 360 min, and the whole calcination process is carried out in nitrogen flow. After the reaction is finished, putting the obtained product into an ethanol solution, performing ultrasonic treatment for 30min, and then centrifuging to remove the redundant graphite-phase carbon nitride material; transferring the obtained product to filter paper, and drying in a vacuum drying oven (60 ℃) to obtain MIL-101/g-C3N4A composite material. The transmission electron microscopy characterization of the composite material is shown in figure 1.
（2）MIL-101/g-C3N4Stability testing in aqueous and acidic solutions
Accurately weighing the MIL-101/g-C prepared above3N450 mg of each of the material and the unmodified MIL-101 material was placed in 5 mL of a nitric acid solution (3.0 mol/L), subjected to ultrasonic oscillation for 10min (power 4000W) in an ultrasonic wave, and then allowed to stand, and the result is shown in FIG. 2 (b). The results show that the unmodified MIL-101 material was almost completely dissolved in the acid solution, and the solution appeared transparent, indicating that the MIL-101 material was unstable in the acid solution due to structural failure. Through g-C3N4Material-wrapped MIL-101/g-C3N4The material is due to g-C of the outer layer3N4The thin film forms an activation energy barrier which needs to be overcome, so that water molecules are effectively prevented from approaching metal ions, and the water system stability of the MIL-101 is improved.
（3）MIL-101/g-C3N4Vitamin extracting and enriching performance
Taking 5.0 mg of MIL-101/g-C3N4Placing the composite material in 5 mL of mixed vitamin solution (the concentration of each vitamin is 10 mg/L), performing ultrasonic treatment for 30min to uniformly disperse the material in the solution to be detected, and then placing the mixed solution in an oscillator for oscillating for 60 min to achieve extraction balance; centrifuging at 4000 rpm for 20min to obtain separated adsorbent material and water phase, measuring the concentration of various vitamins in the mixed vitamins according to national standard, and calculating MIL-101/g-C3N4Adsorption capacity of the composite material to vitamins.
FIG. 4 shows MIL-101/g-C3N4Selective extraction performance of the composite material on vitamins. The experimental results show that g-C3N4Modification of the material may have an effect on the adsorption capacity of the MIL-101 material, but MIL-101/g-C3N4The composite material still shows good selective adsorption performance on vitamin C, and the adsorption capacity of the composite material is 2-3 times that of other vitamins, so that MIL-101/g-C3N4The vitamin has high selective extraction and enrichment performance on the vitamins in different vitamins, and can be used for analytic determination of vitamin C in different vitamin mixed solutions. Separating the MIL-101/g-C3N4Transferring the composite material into a centrifuge tube, adding 50 mu L of acetonitrile solution and 4000WPerforming ultrasonic treatment for 5 min, repeating the above operation for 3 times, mixing desorption solutions, and determining vitamin C concentration in the desorption solution by liquid chromatography. The determination result shows that the concentration of vitamin C in the desorption solution is 3.6 mg/L, namely 1.0 g of MIL-101/g-C3N4The composite material can selectively adsorb 3.6 mg of vitamin C.
Example 3
（1）UIO-66/g-C3N4Preparation of
0.759 g of terephthalic acid was weighed, added to 40 mL of DMF solution, stirred and mixed well, and 1.05 g of ZrCl was added4Mixing with 17 mL of acetic acid by ultrasonic wave uniformly, transferring to a high-temperature reaction kettle, heating in an oven at 120 ℃ for 24 hours, naturally cooling, and performing centrifugal separation to obtain a UIO-66 material;
weighing 5 g of cyanamide, placing the cyanamide into a 50mL porcelain crucible, placing the porcelain crucible into a muffle furnace, calcining the cyanamide at a high temperature for 4 hours at a heating rate of 4 ℃/min and at a temperature of 520 ℃, and cooling the cyanamide to room temperature after the reaction is finished to obtain graphite-phase carbon nitride (g-C)3N4) A material;
mixing UIO-66 with g-C3N4Mixing the materials according to the mass ratio of 1:10, and then placing the mixture in an agate mortar for grinding for 120 min; the mixed material is placed in a tubular furnace with the specification of 120 multiplied by 60 multiplied by 18mm for calcination, the reaction temperature is 500 ℃, the heating rate is 5 ℃/min, the reaction time is 480 min, and the whole calcination process is carried out in nitrogen flow. After the reaction is finished, putting the product into an ethanol solution, performing ultrasonic treatment for 30min, and then centrifuging to remove the redundant graphite phase carbon nitride material; transferring the obtained product to filter paper, and drying in a vacuum drying oven (60 ℃) to obtain UIO-66/g-C3N4A composite material. The transmission electron microscopy characterization of the composite material is shown in figure 1.
（2）UIO-66/g-C3N4Stability testing in aqueous and acidic solutions
Accurately weighing the prepared UIO-66/g-C3N450 mg of each of the material and the unmodified UIO-66 material was placed in 5 mL of a nitric acid solution (5.0 mol/L), subjected to ultrasonic oscillation for 10min (power 4000W) in an ultrasonic wave, and then allowed to stand, and the result is shown in FIG. 2 (c). The results show that the unmodified UIO-66 material is mostly in acid solutionDissolution, indicating that the UIO-66 material is unstable in acid solution. And g-C3N4Material wrapped UIO-66/g-C3N4The material is due to g-C of the outer layer3N4The film forms an activation energy barrier to be overcome, effectively blocks water molecules from entering the UIO-66 material, and effectively improves the water system stability of the UIO-66.
（3）UIO-66/g-C3N4Performance of extracting enriched mercury ion
Mixing 10.0 mg of UIO-66/g-C3N4Placing the composite material in 5 mL of common metal ion mixed solution (pH =2.0, concentration is 20 mg/L), performing ultrasonic treatment for 60 min to uniformly disperse the material in the solution to be detected, and then placing the mixed solution in an oscillator for oscillating for 180 min to achieve extraction balance; centrifuging at 4000 rpm for 20min to obtain separated adsorbing material and water phase, and measuring the concentration of divalent metal ions in the mixed metal solution according to national standard; and calculating UIO-66/g-C3N4Adsorption capacity of the composite material for divalent metal ions.
FIG. 5 is UIO-66/g-C3N4Selective extraction performance for common divalent metal ions. The experimental results show that g-C3N4The modification of the material has little influence on the adsorption capacity of the UIO-66 material, and the UIO-66/g-C3N4The composite material shows good adsorption performance to heavy metal mercury ions in a common divalent metal ion solution, and the adsorption capacity of the composite material is 2-10 times that of other metal ions, so that the UIO-66/g-C3N4The method has high selective extraction and enrichment performance on heavy metal mercury ions in the common divalent metal ion solution, and can be used for analytical determination of mercury ions in the common divalent metal ion solution. Separating the separated UIO-66/g-C3N4Transferring the composite material into a centrifuge tube, adding 200 mu L of nitric acid solution (0.5 mol/L), carrying out ultrasonic treatment at 4000W for 5 min, repeating the operation for 3 times, combining desorption liquid, and measuring the concentration of mercury ions in the desorption liquid by using an inductively coupled plasma emission spectrometer. And (3) measuring results: the concentration of mercury ions in the mixed divalent metal ion solution was 21.7 mg/L, i.e., 1.0 g of UIO-66/g-C3N4Composite materialThe material can selectively adsorb 13.06 mg of mercury ions.

Claims (8)

1. Water system stability MOFs/g-C3N4The preparation method of the composite material comprises the steps of mixing and grinding MOFs material and graphite phase carbon nitride material, and calcining under the action of nitrogen flow; naturally cooling, dispersing in ethanol solution, performing ultrasonic treatment for 20-30 min, centrifuging to remove redundant graphite-phase carbon nitride material, and performing vacuum drying on the product to obtain MOFs/g-C3N4A composite material.
2. The MOFs/g-C for water system stability of claim 13N4The preparation method of the composite material is characterized by comprising the following steps: the MOFs material can be selected from ZIF series materials, MIL series materials and UiO series materials.
3. Water system stability MOFs/g-C according to claim 1 or 23N4The preparation method of the composite material is characterized by comprising the following steps: the mass ratio of the MOFs material to the graphite-phase carbon nitride material is 100: 1-0.1: 1.
4. Water system stability MOFs/g-C according to claim 1 or 23N4The preparation method of the composite material is characterized by comprising the following steps: and grinding is carried out in an agate mortar, and the grinding time is 30-120 min.
5. Water system stability MOFs/g-C according to claim 1 or 23N4The preparation method of the composite material is characterized by comprising the following steps: the calcination temperature is 200-500 ℃, the heating rate is 1-5 ℃/min, and the calcination time is 120-480 min.
6. Water system stable MOFs/g-C prepared by the method of claim 13N4The application of the composite material in extraction, enrichment and detection of lanthanide ytterbium is characterized in that: the MOFs/g-C3N4The composite material is ZIF-67/g-C3N4。
7. Water system stable MOFs/g-C prepared by the method of claim 13N4The application of the composite material in the extraction, enrichment and detection of vitamin C is characterized in that: the MOFs/g-C3N4The composite material is MIL-101/g-C3N4。
8. Water system stable MOFs/g-C prepared by the method of claim 13N4The application of the composite material in the extraction, enrichment and detection of the mercury ions is characterized in that: the MOFs/g-C3N4The composite material is UIO-66/g-C3N4。
CN202210263346.5A 2022-03-17 2022-03-17 Preparation and application of MOFs/graphite phase carbon nitride composite material with water system stability Active CN114570334B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210263346.5A CN114570334B (en) 2022-03-17 2022-03-17 Preparation and application of MOFs/graphite phase carbon nitride composite material with water system stability

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210263346.5A CN114570334B (en) 2022-03-17 2022-03-17 Preparation and application of MOFs/graphite phase carbon nitride composite material with water system stability

Publications (2)

Publication Number Publication Date
CN114570334A true CN114570334A (en) 2022-06-03
CN114570334B CN114570334B (en) 2023-04-25

Family

ID=81779606

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210263346.5A Active CN114570334B (en) 2022-03-17 2022-03-17 Preparation and application of MOFs/graphite phase carbon nitride composite material with water system stability

Country Status (1)

Country Link
CN (1) CN114570334B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104475030A (en) * 2014-11-20 2015-04-01 杭州电子科技大学 Preparation method of magnetic metal organic framework material and application of magnetic metal organic framework material
CN105107467A (en) * 2015-10-09 2015-12-02 南昌航空大学 Preparation and novel application of a type of MIL-101(Cr) adsorbent modified by virtue of post translation
CN105175295A (en) * 2015-09-24 2015-12-23 南昌航空大学 Preparation for thiol-functionalization MOFs material and application thereof in adsorption and removal of heavy metal ions in water
CN106501332A (en) * 2016-11-06 2017-03-15 桂林理工大学 Zn MOFs/ glass-carbon electrodes and preparation method thereof and application
CN110026242A (en) * 2019-05-10 2019-07-19 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of Co/Ce bimetallic MOF base ozone catalyst and products thereof and application
CN111250142A (en) * 2020-03-31 2020-06-09 上海电力大学 Preparation method, product and application of graphite-phase carbon nitride/high-iodine bismuth oxyiodide heterojunction with up-conversion characteristic
CN112108121A (en) * 2020-09-28 2020-12-22 南京林业大学 Magnetic Fe3O4Preparation method of @ MOF composite material, product and application thereof
CN112169768A (en) * 2020-09-30 2021-01-05 东华大学 Preparation method of metal organic framework/graphite-like phase carbon nitride composite material
CN114672034A (en) * 2022-03-11 2022-06-28 东北大学 Method for preparing MOFs material by thermally-assisted mechanical ball milling method
WO2022141653A1 (en) * 2020-12-29 2022-07-07 南京师范大学 Detection system for detecting t-2 toxin residue, and preparation method therefor and use thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104475030A (en) * 2014-11-20 2015-04-01 杭州电子科技大学 Preparation method of magnetic metal organic framework material and application of magnetic metal organic framework material
CN105175295A (en) * 2015-09-24 2015-12-23 南昌航空大学 Preparation for thiol-functionalization MOFs material and application thereof in adsorption and removal of heavy metal ions in water
CN105107467A (en) * 2015-10-09 2015-12-02 南昌航空大学 Preparation and novel application of a type of MIL-101(Cr) adsorbent modified by virtue of post translation
CN106501332A (en) * 2016-11-06 2017-03-15 桂林理工大学 Zn MOFs/ glass-carbon electrodes and preparation method thereof and application
CN110026242A (en) * 2019-05-10 2019-07-19 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of Co/Ce bimetallic MOF base ozone catalyst and products thereof and application
CN111250142A (en) * 2020-03-31 2020-06-09 上海电力大学 Preparation method, product and application of graphite-phase carbon nitride/high-iodine bismuth oxyiodide heterojunction with up-conversion characteristic
CN112108121A (en) * 2020-09-28 2020-12-22 南京林业大学 Magnetic Fe3O4Preparation method of @ MOF composite material, product and application thereof
CN112169768A (en) * 2020-09-30 2021-01-05 东华大学 Preparation method of metal organic framework/graphite-like phase carbon nitride composite material
WO2022141653A1 (en) * 2020-12-29 2022-07-07 南京师范大学 Detection system for detecting t-2 toxin residue, and preparation method therefor and use thereof
CN114672034A (en) * 2022-03-11 2022-06-28 东北大学 Method for preparing MOFs material by thermally-assisted mechanical ball milling method

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
NING ZHANG ET AL.: "Moisture stable Ni-Zn MOF/g-C3N4 nanoflowers: A highly efficient adsorbent for solid-phase microextraction of PAHs", 《JOURNAL OF CHROMATOGRAPHY A》 *
RONG WANG ET AL.: "Quasi-Polymeric Metal-Organic Frameworks UiO-66/g-C3N4 heterojunctions for enhanced photocatalytic hydrogen evolution under visible light irradiation", 《ADVANCED MATERIALS》 *
WU JIAO ET AL.: "Adsorption performance and mechanism of g-C3N4/UiO-66 composite for U(VI) from aqueous solution" *
XUEWEI WANG ET AL.: "Rapid synthesis of graphite phase carbon nitride/zeolitic imidazolate framework-8 with hierarchical structure and its superior adsorption of polycyclic aromatic hydrocarbons from aqueous solution", 《JOURNAL OF CHROMATOGRAPHY A》 *
丁琳: "MIL-101和Zr-MOFs改性与煅烧材料的制备及其去除重金属性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
宋银银: "吡唑羧酸类小配体构筑介孔金属有机框架", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
张鹏萍: "基于氮化碳纳米材料电化学发光的研究及其应用" *
王茀学: "g-C3N4@Zn-MOF复合材料的制备及其光催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
秦武军: "冠醚功能化氧化石墨烯对Sr(Ⅱ)的选择性萃取与检测", 《化学研究与应用》 *

Also Published As

Publication number Publication date
CN114570334B (en) 2023-04-25

Similar Documents

Publication Publication Date Title
Gao et al. Development and application of vortex-assisted membrane extraction based on metal–organic framework mixed-matrix membrane for the analysis of estrogens in human urine
Lin et al. Magnetic metal–organic framework nanocomposites for enrichment and direct detection of small molecules by negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry
Zhang et al. Synthesis of adenosine functionalized metal immobilized magnetic nanoparticles for highly selective and sensitive enrichment of phosphopeptides
CN108751189A (en) The preparation and application of the aluminium base MOF porous carbon materials of high-specific surface area
CN108404868A (en) NH is adulterated based on alkali metal cation2- MIL-125 (Ti) materials and preparation method
CN105621389A (en) Supported composite carbon molecular sieve membrane
WO2023078376A1 (en) Application of carboxylated covalent organic magnetic framework material as magnetic solid-phase extraction adsorbent
Wang et al. Cobalt-based zeolitic imidazolate frameworks modified separator as efficient polysulfide adsorbent for high performance lithium-sulfur batteries
CN109444250A (en) A kind of preparation of graphene/porous carbon complex and mass spectral analysis application of double heteroatoms doping
Li et al. Comparative evaluation of MAX-Ti 3 AlC 2 and MXene-Ti 3 C 2 as affinity chromatographic materials for highly selective enrichment of phosphopeptides
CN110394159A (en) The method and its application of one-step method preparation ion exchange ZIF-8 adsorbent
CN111282545B (en) Two-dimensional van der waals heterojunction and application thereof
CN109731551A (en) A kind of metallic organic frame films extract the application of helium in rich-helium type natural gas
CN111196602B (en) Preparation method and application of double-heteroatom-doped porous graphene-like nano carbon sheet
CN114713196A (en) Preparation and application of metal organic framework derived bimetallic oxide magnetic carbon material
CN106984137A (en) A kind of absorption CO of phase separation2Polyaminoacid ionic liquid preparation and its application method
CN114570334A (en) Preparation and application of water system stability MOFs/graphite phase carbon nitride composite material
CN105624421A (en) Method for separating palladium from aqueous solution through dinitrogen amide hydrazone pyridine ramifications
CN111672474A (en) Magnetic nitrogen-doped carbon oxide nanotube material and preparation method and application thereof
CN115518621B (en) Preparation and application of corn cob-shaped metal-organic framework material inlaid metal oxide carbon material
WO2022088675A1 (en) Carbon dioxide adsorbent, and preparation method and use method therefor
Wang et al. Toward Practical Lithium-Air Batteries by Avoiding Negative Effects of CO2
CN112079348B (en) Preparation method and application of graphene/MOF derived sulfide composite aerogel
Zhou et al. An alkali-resistant zirconium-biligand organic framework with dual-metal centers for highly selective capture of phosphopeptides
CN113680325A (en) Preparation method and application of diamine-modified MOF/GO alkene composite adsorbent

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant