CN111375386A - Functionalized magnetic MOF composite nano material, preparation thereof and nuclear industrial application thereof - Google Patents

Functionalized magnetic MOF composite nano material, preparation thereof and nuclear industrial application thereof Download PDF

Info

Publication number
CN111375386A
CN111375386A CN202010451860.2A CN202010451860A CN111375386A CN 111375386 A CN111375386 A CN 111375386A CN 202010451860 A CN202010451860 A CN 202010451860A CN 111375386 A CN111375386 A CN 111375386A
Authority
CN
China
Prior art keywords
sio
uio
nps
adsorption
functionalized magnetic
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
CN202010451860.2A
Other languages
Chinese (zh)
Other versions
CN111375386B (en
Inventor
李祎亮
毕常芬
原野
侯文彬
宁洪鑫
魏会强
勾文峰
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.)
Institute of Radiation Medicine of CAMMS
Original Assignee
Institute of Radiation Medicine of CAMMS
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 Institute of Radiation Medicine of CAMMS filed Critical Institute of Radiation Medicine of CAMMS
Publication of CN111375386A publication Critical patent/CN111375386A/en
Application granted granted Critical
Publication of CN111375386B publication Critical patent/CN111375386B/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
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Compounds Of Iron (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention prepares a novel phytic acid functionalized magnetic MOF composite nano material I (Fe)3O4@SiO2@ UiO-66-PA), which has the advantages of MOF materials and magnetic nano materials, and shows good adsorption performance and application prospect in the aspect of removing uranium from radioactive wastewater.

Description

Functionalized magnetic MOF composite nano material, preparation thereof and nuclear industrial application thereof
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a functionalized magnetic MOF composite nano material, preparation thereof and application thereof in radioactive wastewater treatment.
Background
The nuclear energy is high-efficiency, clean and low-carbon energy, and the strategic requirements of national energy structure, energy safety guarantee, environmental protection and emission reduction are met by vigorously developing the nuclear energy. Along with the positive promotion of nuclear power construction, the energy supply and safety are guaranteed, the environment is protected, the structural optimization and the sustainable development of the power industry are realized, and the method becomes an important national policy of Chinese energy construction. The development of nuclear power must also face the problem of disposal of the radionuclide waste. A plurality of radioactive elements and a plurality of heavy metal ions exist in the radioactive wastewater containing uranium, and when the system is acidic, UO is mainly used2 2+The form exists, and the radionuclide can cause various injuries and pathogenic effects after entering organisms and human bodies, and can seriously cause ecological disasters. How to fully utilize nuclear energy and safely treat a large amount of nuclear waste liquid to protect ecological safety is a difficult problem which needs to be overcome urgently in various countries at present. The existing technical method for treating the nuclear waste liquid has various defects (such as low adsorption quantity, difficult recycling and the like), and the magnetic MOF composite nano material has stable MOF layer framework and diversified adjustable and controllable functions on one hand, and can be quickly and effectively separated from a purification medium on the other hand, so that the research on the application of the novel functional magnetic MOF material in the removal of radioactive nuclides in the nuclear waste liquid has important significance for the sustainable development of nuclear energy.
At present, methods for treating radioactive wastewater include a coagulation precipitation method, an evaporation concentration method, a membrane separation method, an ion exchange method, a biological method, an adsorption method, and the like. However, most of these methods have certain disadvantages, for example, the precipitation method is easy to generate a large amount of sludge, the photocatalytic degradation can generate some byproducts, and the adsorption method is widely applied to radioactive sewage treatment due to the advantages of simple operation, low cost, easy large-scale application and the like. In recent decades, researchers have been working on novel adsorption materials for radionuclides in water, including mesoporous materials, solid waste derived adsorbents, covalent organic frameworks, graphene oxides, microorganisms, and metal-organic frameworks.
Metal Organic Frameworks (MOFs) are a novel porous material and are formed by bridging Metal ions or Metal ion clusters and various Organic ligands. Compared with the traditional porous material, the MOF material has the advantages of large specific surface area, high porosity, diversified and adjustable structure and function and the like, and has great application prospect in a plurality of fields such as storage, drug delivery, separation, catalysis and the like. Among them, three kinds of MOFs materials, ZIFs (Zeolite Imidazolate frameworks), MILs (materials of Institute Lavoisier), UiOs (university of Oslo), are not collapsed in the framework structure of water, and have better stability. The wastewater generated by the nuclear industry is in a very low pH range, the Zr-MOF material (comprising UiO-66) formed by zirconium ions and terephthalic acid or derivatives thereof has the tolerance to strong acid and medium alkalinity, and the Zr-MOF material attracts special attention of researchers and is applied to the adsorption research of radionuclide U. E.g., UiO-66 and UiO-66-NH2The adsorption capacity for U (VI) in the water body is 109.9 and 114.9 mg/g. The adsorption capacity of the ammoxim-modified UiO-66-AO to U (VI) was 227.8 mg/g. Scientists believe that the stability, the multifunctional modification and the mild synthesis condition of the UiO-66 structure have good development prospect when used for adsorbing uranium. However, the difficult separation, slow adsorption kinetics, led to the UiO-66 series of materials still in the first phase for research applications in nuclear species adsorption.
In recent years, researchers have successfully developed various magnetic composite adsorbing materials for removing nuclides in radioactive wastewater. Such as magnetic M-Fe/Zn-LDO @ CNTs, amino modified magnetic graphene and Fe3O4@ZIF-8、Fe3O4The @ AMCA-MIL-53 composite material can quickly and effectively remove U (VI) in the water body. The magnetic nano material has the advantages of large surface area, small particle size, superparamagnetism, no toxicity, mild preparation condition, low cost and the like, and the magnetic nano composite material isThe material can be recovered under an external magnetic field, and the problem that the traditional adsorbing material is difficult to separate is solved. However, the adsorption capacity, selectivity, etc. of the magnetic composite material are still to be further improved. The assembled UiO-66-AO after the post-modification of the ammoxim group can quickly and effectively remove 99 percent of U (VI) in seawater containing U500ppb within 10 min. Magnetic UiO-66 series composite materials (e.g. Fe)3O4@SiO2@Zr-MOF、Fe3O4@ UiO-66) is applied to the field of research on removal of pollutants in water bodies, but few documents are reported in the aspect of radioactive wastewater treatment. How to combine the UO-66 series materials with magnetism and carry out reasonable functional modification to prepare the functional magnetic MOF composite nano material with high adsorption performance and strong magnetism, and the method has certain innovation and practical application value in the aspect of preparing radionuclide adsorption materials.
In view of the above, the phosphoric acid functionalized magnetic MOF composite nanometer material is prepared and used for uranium adsorption performance and mechanism research. The influence of pH, adsorption time, adsorption temperature, initial concentration and the like of the solution on the adsorption effect is explored by adopting a static method, the adsorption performance of the material on nuclides is studied, an adsorption reaction kinetic model, a thermodynamic model and the like are analyzed, and the adsorption mechanism is further explained. Optimizing adsorption conditions, researching factors influencing adsorption efficiency and improving adsorption application performance. The research can provide referential thought and approach for the research of the radioactive wastewater adsorbent.
The terms in the present invention explain: MOF is an abbreviation for metal organic framework compound (english name metalorganic framework); NPs are short for Nanoparticles (nanoparticules).
Disclosure of Invention
The invention prepares a novel functional magnetic MOF composite material (Fe)3O4@SiO2@ UiO-66-PANPs) and a series of evaluations are carried out on the performance of the material in removing U (VI) in the water body, and the TEM representation is shown in the attached figure 2 of the specification.
The invention discloses a composite material I, and the preparation process is shown in the attached figure 17 of the specification.
The invention also discloses a preparation method of the composite material I, which comprises the following steps:
FeCl is added3·6H2O、CH3COONH4Mixing sodium citrate, adding into ethylene glycol, ultrasonic dispersing to obtain homogeneous phase, transferring into Teflon-lined reaction kettle, reacting, cooling, washing with water and ethanol, and vacuum drying to obtain Fe3O4NPs；
Fe3O4NPs are dispersed in water, ammonia water and ethanol are mixed and then added into a reaction system, ultrasonic dispersion is uniform, TEOS is slowly dripped into the reaction system, stirring is carried out, washing is carried out by water and ethanol respectively, and vacuum drying is carried out, thus obtaining Fe3O4@SiO2NPs；
Fe3O4@SiO2NPs with 466mg ZrCl4Dispersing in DMF, dissolving 2-amino terephthalic acid in another part of DMF, ultrasonic mixing, reacting, cooling, washing with DMF and methanol respectively, standing with methanol to soak the activated material, and drying to obtain Fe3O4@SiO2@UiO-66-NH2NPs；
Sodium phytate and CH3COOH solution was mixed and Fe was added3O4@SiO2@UiO-66-NH2NPs, adjusting the pH value of a reaction system, reacting, cooling, washing to be neutral, and drying to obtain Fe3O4@SiO2@ UiO-66-PANPs, composite I of the present invention.
Further, the invention records the research on the adsorption performance and mechanism of the composite material I on the radionuclide U in the water body.
Still further, composite I of the present invention, includes but is not limited to the following advantages:
(1) stability and multi-site modifiability;
(2) has superparamagnetism;
(3) strong acid-base tolerance, thermal stability and structural function modifiability;
(4) has stronger acting force with the binding site of the radionuclide U (VI), and shows higher adsorption quantity and higher adsorption capacity.
Drawings
FIG. 1 is Fe3O4@SiO2@UiO-66-NH2TEM and EDX images of;
FIG. 2 is Fe3O4@SiO2TEM and EDX images of @ UiO-66-PA;
FIG. 3 is Fe3O4@SiO2TEM and EDX patterns after adsorption of U (VI) by @ UiO-66-PA;
FIG. 4 is Fe3O4@SiO2(a)，Fe3O4@SiO2@UiO-66-NH2(b) And Fe3O4@SiO2FT-IR chart of @ UiO-66-PA (c);
FIG. 5 is Fe3O4@SiO2N of @ UiO-66-PA2Adsorption and desorption isotherm graphs;
FIG. 6 is Fe3O4@SiO2A VSM plot of @ UiO-66-PA;
FIG. 7 shows Fe at different pH values3O4@SiO2@UiO-66-NH2(a) And Fe3O4@SiO2Zeta potential value diagram of @ UiO-66-PA (b);
FIG. 8 shows Fe in initial solutions of different U (VI)3O4@SiO2@UiO-66-NH2(a) And Fe3O4@SiO2@ UiO-66-PA (b) adsorption capacity plot;
FIG. 9 shows Fe at different adsorption times3O4@SiO2@UiO-66-NH2(a) And Fe3O4@SiO2An adsorption capacity plot of @ UiO-66-PA (b) versus U (VI);
FIG. 10 is a graph of a quasi-first order kinetic model fit;
FIG. 11 is a graph of a quasi-secondary kinetic model fit;
FIG. 12 shows Fe at different temperatures3O4@SiO2Adsorption isotherm plot of @ UiO-66-PA;
FIG. 13 is a plot of the fitted Langmuir and Freundlich adsorption isotherms;
FIG. 14 is solution ionic strength vs. Fe3O4@SiO2Influence graph of the adsorption capacity of @ UiO-66-PA;
FIG. 15 is a drawing showingFe3O4@SiO2The adsorption selectivity profile of @ UiO-66-PA to U (VI);
FIG. 16 is Fe3O4@SiO2Graph of desorption effect of @ UiO-66-PA;
FIG. 17 is a schematic diagram of the preparation process of composite material I according to the present invention.
Examples
Example 1 Fe3O4@SiO2@UiO-66-PA NPsPreparation of
1、Fe3O4Preparation of NPs
2.70g FeCl3·6H2O，7.71g CH3COONH40.80g of sodium citrate is mixed and then added into 140mL of glycol, the mixture is ultrasonically dispersed into a uniform phase, the uniform phase is transferred into a Teflon-lined reaction kettle, the reaction is carried out for 16h at 200 ℃, the mixture is naturally cooled to the room temperature, washed by ultrapure water for 3 times, washed by absolute ethyl alcohol for 3 times, and dried in vacuum at 40 ℃ to obtain Fe3O4NPs。
2、Fe3O4@SiO2Preparation of NPs
300mg Fe3O4NPs are ultrasonically dispersed in 12mL of ultrapure water, 0.75mL (30%, v/v) of ammonia water and 46mL of ethanol are mixed and then added into a reaction system, the ultrasonic dispersion is uniform, 0.9mL of TEOS is diluted in 3mL of ethanol and slowly dripped into the reaction system, the mixture is vigorously stirred at room temperature (25 ℃) for 12 hours, the ultrapure water is washed to be neutral, the absolute ethanol is washed for 3 times, and the mixture is dried in vacuum at 50 ℃ to obtain Fe3O4@SiO2NPs。
3、Fe3O4@SiO2@UiO-66-NH2Preparation of NPs
200mg Fe3O4@SiO2NPs with 466mg ZrCl4Uniformly dispersing in 30mL of DMF by ultrasonic, dissolving 362mg of 2-amino terephthalic acid in another 30mL of DMF, uniformly mixing the reaction system by ultrasonic, reacting at 120 ℃ for 6h, naturally cooling to room temperature, washing with DMF for 3 times, washing with anhydrous methanol for 3 times, standing with anhydrous methanol to soak the activated material, changing the solution once every 8h, activating for 3d, and vacuum drying at 40 ℃ to obtain Fe3O4@SiO2@UiO-66-NH2NPs。
4、Fe3O4@SiO2Preparation of @ UiO-66-PA NPs
15mg sodium phytate dissolved in 4mL ultrapure water and 20mL 2% (v/v) CH3COOH solution mixed, 40mg Fe3O4@SiO2@UiO-66-NH2NPs are added into the system for uniform ultrasonic dispersion, the pH of the reaction system is adjusted to 5, the reaction is carried out for 30min at 50 ℃, then the reaction is carried out for 12h at 115 ℃, the reaction is naturally cooled to room temperature, ultrapure water is washed to be neutral, and vacuum drying is carried out at 40 ℃ to obtain Fe3O4@SiO2@ UiO-66-PANPs, composite I of the present invention.
Example 2 TEM characterization
The instrument model is as follows: JEM-2100(Japan) Transmission Electron microscope
Fe of example 13O4@SiO2@UiO-66-NH2，Fe3O4@SiO2@ UiO-66-PA for adsorbing Fe of U (VI)3O4@SiO2@ UiO-66-PA TEM and EDX characterization were performed according to the prior art. The results are shown in the attached figures 1, 2 and 3 of the specification.
From FIG. 1, Fe can be seen3O4@SiO2The diameter of the NPs is 240-300nm, and 40nm SiO exists on the outer layer of the NPs2Layer of SiO2Coated with 50nm thick UiO-66-NH2The Zr element is uniformly dispersed on the surface of the nanoparticles.
From FIG. 2, it can be seen that the phosphate group is Fe after phytic acid modification3O4@SiO2@UiO-66-NH2The surface of the NPs is successfully modified. Meanwhile, the silicon layer is partially dissolved, but the nanostructure of the iron oxide is not damaged, and some silicon-containing particles penetrate into the MOF mesopores, and the mesopore structure is beneficial to the adsorption of the nanocomposite material.
From FIG. 3, Fe can be seen3O4@SiO2After the @ UiO-66-PANPs adsorb U (VI), the elements P, Zr and U are uniformly distributed on the surface of the nano-particles, which indicates that Fe3O4@SiO2@ UiO-66-PANPs successfully capture U (VI), and the structure of the nano material is kept stable.
Example 3 FT-IR characterization
The instrument model is as follows: BRUKER TENSOR 27 Fourier transform infrared spectrophotometer
Fe of example 13O4@SiO2，Fe3O4@SiO2@UiO-66-NH2And Fe3O4@SiO2@ UiO-66-PA was subjected to FT-IR characterization according to the prior art. The results are shown in figure 4 of the specification.
It can be seen from FIG. 4 that in Fe3O4@SiO2NPs (a) spectrum at 590cm-1The peak at (B) is attributed to the stretching vibration of Fe-O bond, 1086cm-1The peak at (A) is derived from stretching vibration of Si-O-Si, and 1628cm-1At a position of 3431cm-1The absorption peaks at (a) correspond to stretching vibration of a C ═ O bond and stretching vibration of an O — H or N — H bond, respectively. After modification of the MOF layer, Fe3O4@SiO2@UiO-66-NH2NPs (b) infrared spectrum shows new absorption peak, 1428cm-1、1506cm-1And 1572cm-1Respectively, the absorption peak of stretching vibration of C-O, C ═ C, N-H bond in the MOF layer. In FIG. c, 1055em-1The characteristic stretching vibration absorption peak of the bond P ═ O indicates the successful modification of the phosphate group.
Example 4N2Characterization by adsorption-desorption
The instrument model is as follows: micromeritics ASAP (USA)2010Apparatus
Fe of example 13O4@SiO2@ UiO-66-PA N according to the existing method2And (5) performing adsorption-desorption characterization. The results are shown in figure 5 of the specification.
From FIG. 5, Fe can be seen3O4@SiO2The isotherm of @ UiO-66-PANPs is type IV, indicating a mesoporous structure. Using the Brunauer-Emmett-Teller (BET) method in terms of N2The specific surface area, the total pore volume and the pore diameter of the adsorbing material are respectively 182.8m by the adsorption isotherm calculation2/g，0.149cm3G and 3.19nm, demonstrating the mesoporous structure of the MOF layer.
Example 5 VSM characterization
The instrument model is as follows: LDJ9600-1(USA) vibration sample magnetometer
Fe of example 13O4@SiO2The VSM characterization was performed according to the current method at @ UiO-66-PA. The results are shown in figure 6 of the specification.
From FIG. 6, Fe can be seen3O4@SiO2@ UiO-66-PA NPs are paramagnetic, saturated magnetizations (M)s) The value was 53.19emu g-1Description of Fe3O4@SiO2@ UiO-66-PANPs can be easily separated by means of an external magnetic field and quickly redispersed after removal of the magnetic field, which facilitates their use for the adsorption of uranium (VI) in aqueous solution.
Example 6 Zeta potential characterization
The instrument model is as follows: brookhaven Zeta PALS (USA) analyzer
Fe of example 13O4@SiO2@UiO-66-NH2And Fe3O4@SiO2The Zeta potential characterization is carried out according to the prior method at @ UiO-66-PA. The results are shown in figure 7 of the specification.
From FIG. 7, Fe can be seen3O4@SiO2@UiO-66-NH2The surface charge of NPs does not change significantly over a large pH range (1.5-5.5), while Fe3O4@SiO2@ UiO-66-PANPs have a large change in surface charge due to surface modification of phosphate groups. Fe3O4@SiO2@ UiO-66-PANPs have an isoelectric point of about 3.1, a surface exhibiting electronegativity at pH values greater than 3.1, and Fe at pH 5.03O4@SiO2The Zeta potential of @ UiO-66-PANPs is-17.6 mV. Fe3O4@SiO2The higher surface electronegativity of the @ UiO-66-PANPs is favorable for avoiding agglomeration among nano-particles and is helpful for UO2(OH)+The plasma moves to the surface of the material rapidly, and the rapid capture of U (VI) by the nano material is promoted.
Example 7 Effect of solution pH on adsorption Capacity
The instrument model is as follows: UV-2600(A) ultraviolet visible spectrophotometer
Fe of example 13O4@SiO2@UiO-66-NH2And Fe3O4@SiO2@ UiO-66-PA the adsorption capacity for U (VI) was determined at different pH values. The results are shown in figure 8 of the specification.
From FIG. 8, Fe can be seen3O4@SiO2The adsorption capacity of @ UiO-66-PA NPs (b) for U (VI) increases rapidly with increasing pH, and Fe at pH 5.03O4@SiO2The adsorption quantity of the @ UiO-66-PANPs to U (VI) reaches the maximum value of 249.5mg/g (q)e). At the same time, Fe3O4@SiO2@UiO-66-NH2The adsorption amount of nps (a) to u (vi) did not change significantly with increasing pH, and was 27.69mg/g at pH 5.0.
Example 8 Effect of adsorption time on adsorption Capacity
The instrument model is as follows: UV-2600(A) ultraviolet visible spectrophotometer
Fe of example 13O4@SiO2@UiO-66-NH2And Fe3O4@SiO2@ UiO-66-PA adsorption capacity was measured under different adsorption time conditions. The results are shown in figure 9 of the specification.
From FIG. 9, it can be seen that Fe is present at about 15min3O4@SiO2The adsorption of @ UiO-66-PA NPs (b) to U (VI) reaches equilibrium rapidly due to Fe3O4@SiO2Strong complexation between the phosphate groups on the surface of @ UiO-66-PA NPs and U (VI).
Example 9U (VI) Effect of initial concentration on adsorption Capacity
The instrument model is as follows: UV-2600(A) ultraviolet visible spectrophotometer
Fe of example 13O4@SiO2@ UiO-66-PA the adsorption capacity was determined at different initial U (VI) concentrations. The results are shown in figure 12 of the specification.
It can be seen from FIG. 12 that as the initial U (VI) concentration was gradually increased from 20mg/L, the amount adsorbed also increased significantly. When the initial concentration of U (VI) is 200mg/L, Fe3O4@SiO2The adsorption capacity of @ UiO-66-PA for U (VI) reaches a maximum.
EXAMPLE 10 Effect of temperature on adsorption Capacity
The instrument model is as follows: UV-2600(A) ultraviolet visible spectrophotometer
Fe of example 13O4@SiO2@ UiO-66-PA was characterized for U (VI) adsorption capacity at different temperatures and compared to other magnetic adsorbents for performance. The results are shown in FIG. 12 and Table 1 in the specification.
Figure BDA0002506230910000081
Table 1: adsorption effect of different nano adsorption materials
It can be seen from FIG. 12 that Fe increases with temperature3O4@SiO2Increased U (VI) adsorption of @ UiO-66-PANPs due to Fe3O4@SiO2The adsorption thermodynamics of @ UiO-66-PANPs for U (VI) is a spontaneous endothermic process. At the same time, Fe3O4@SiO2The @ UiO-66-PANPs grafted phosphate groups allow the adsorbent to have a higher adsorption capacity (320.3mg/g) and adsorption rate (15 min). As can be seen from Table 1, Fe3O4@SiO2The adsorption capacity, adsorption rate and selectivity of @ UiO-66-PANPs were higher than those of other partial magnetic adsorbents (Table 1).
EXAMPLE 11 screening of different reaction conditions
Preparing the nano material at different reaction temperatures and component ratios, and carrying out condition screening and ratio optimization. The results are shown in Table 2.
Figure BDA0002506230910000091
Table 2: fe3O4@SiO2Screening of conditions for preparation of @ UiO-66-PA
As can be seen from Table 2, when the amount of sodium phytate in the preparation process is fixed, the adsorption amount of the material to U (VI) is increased along with the increase of the temperature, the maximum adsorption amount is obtained when the amount of sodium phytate is 15mg at 115 ℃, but the adsorption amount of the material is reduced along with the increase of the temperature or the amount of sodium phytate, which is attributed to the fact that the reaction system is increased in acidity by high content of sodium phytate, so that the structure of the material is damaged.
Example 12 Material adsorption kinetics model fitting
And fitting the adsorption kinetic model to the material, and obtaining the relevant parameters of the pseudo first-order model and the pseudo second-order model. The results are shown in fig. 10, fig. 11, and table 3.
Figure BDA0002506230910000092
Table 3: fe3O4@SiO2Kinetic model constants for adsorbing U (VI) by @ UiO-66-PA
As can be seen from fig. 10, fig. 11 and table 3, the fitting curve variance of the material pseudo second-order model is 0.9999, which shows that the adsorption kinetic model of the material is closer to the pseudo second-order model, and meanwhile, q obtained from the pseudo second-order modelecal (244.50mg/g) value close to qe，exp(245.79mg/g) further elucidating that the adsorption process follows a pseudo-second order model, indicating that uranium is in Fe3O4@SiO2Adsorption on @ UiO-66-PANPs is a chemisorption process.
Example 13 material adsorption thermodynamic model fitting
Fitting an adsorption thermodynamic model to the material, obtaining relevant parameters of a Langmuir model and a Freundlich model, and calculating delta S by using a Van' tHoff equation and a Gibb free energy function0(entropy change), Δ H0(enthalpy change) and Δ G0Thermodynamic parameters (gibbs free energy change) to reveal whether the adsorption process is an endothermic process or an exothermic process, a spontaneous or non-spontaneous process. The results are shown in fig. 13, table 4, and table 5.
Figure BDA0002506230910000101
Table 4: adsorption constants of Langmuir and Freundlich
Figure BDA0002506230910000102
Table 5: thermodynamic parameters of adsorption
As can be seen from FIGS. 13 and Table 4, R is the same as2The value is higher, the adsorption process follows a Langmuir isotherm model, and U (VI) is shown in Fe3O4@SiO2Adsorption on @ UiO-66-PA NPs is a monolayer surface complexation process. As can be seen from Table 5, a positive Δ H0Values prove that U (VI) is in Fe3O4@SiO2Adsorption on @ UiO-66-PANPs is endothermic, with a positive Δ S0Indicating that the randomness of the solid-liquid interface increases during the adsorption process, positive Δ G0Indicating that the adsorption process is spontaneous, Fe3O4@SiO2@ UiO-66-PANPs have a high affinity for U (VI) in aqueous solution. Δ G0The values decrease with increasing temperature, indicating that the higher the temperature, U (VI) is in Fe3O4@SiO2The higher the spontaneous tendency of adsorption on @ UiO-66-PANPs.
EXAMPLE 14 Effect of ions in solution on adsorption Capacity
The instrument model is as follows: UV-2600(A) ultraviolet visible spectrophotometer
Fe of example 13O4@SiO2@ UiO-66-PA was used for adsorption capacity characterization under different ionic strength conditions. The results are shown in figure 14 of the specification.
As can be seen from FIG. 14, in the NaCl concentration range of 0.1-0.5mol/L, the adsorption capacity decreases by about 18%, which is probably caused by the decrease in ion transport rate and the interference of electrostatic interaction due to the higher NaCl concentration.
Example 15 Effect of competing ions in solution on adsorption selectivity
The instrument model is as follows: ELEMENT 2 high resolution inductively coupled plasma mass spectrometer
Fe of example 13O4@SiO2@ UiO-66-PA for adsorptive selectivity characterization under conditions containing competing ions. The results are shown in FIG. 15 of the specification.
As can be seen from FIG. 15, Fe3O4@SiO2The adsorption capacity of @ UiO-66-PANPs to U (VI) is significantly higher than that of other coexisting metal ions. Fe3O4@SiO2S selectivity of @ UiO-66-PANPs to uraniumuThe value was 82.3%, indicating good selectivity to U (VI). Fe3O4@SiO2The capture effect of the @ UiO-66-PA NPs on U (VI) depends on the chelation of the phosphate group modified on the surface of the material and the U (VI). Fe when various metal ions coexist because the phosphate group is more easily coordinated with actinides in water3O4@SiO2The adsorption selectivity of @ UiO-66-PA NPs to U (VI) still performed well.
Example 16 evaluation of Material Desorption conditions
The instrument model is as follows: UV-2600(A) ultraviolet visible spectrophotometer
Fe of example 13O4@SiO2The desorption performance characterization is carried out on the @ UiO-66-PA, and a proper eluent is selected to carry out the desorption on the Fe loaded with the uranium3O4@SiO2Stripping uranium from @ UiO-66-PA provides better U (VI) recovery. The results are shown in FIG. 16 of the specification.
As can be seen from FIG. 16, different 0.01M acidic solutions (H) were used2SO4HCl and HNO3) Fe loaded with U (VI) was analyzed3O4@SiO2Effect of U (VI) desorption in @ UiO-66-PA, H2SO4HCl and HNO3The desorption rates of (a) were 94.21, 81.50 and 25.36%, respectively. The results show that: 0.01M H2SO4The solution is more suitable for desorption of u (vi) from the material.

Claims (9)

1. Functionalized magnetic MOF composite nano material I (Fe)3O4@SiO2@UiO-66-PA)。
2. The functionalized magnetic MOF composite nanomaterial I of claim 1, wherein TEM representation thereof is shown in figure 2 in the specification.
3. The functionalized magnetic MOF composite nanomaterial I of claims 1-2, prepared by the following method:
FeCl is added3·6H2O、CH3COONH4Sodium citrateMixing, adding into ethylene glycol, ultrasonic dispersing to obtain uniform phase, transferring into Teflon-lined reaction kettle, reacting, cooling, washing with water and ethanol, and vacuum drying to obtain Fe3O4NPs；
Fe3O4NPs are dispersed in water, ammonia water and ethanol are mixed and then added into a reaction system, ultrasonic dispersion is uniform, TEOS is slowly dripped into the reaction system, stirring is carried out, washing is carried out by water and ethanol respectively, and vacuum drying is carried out, thus obtaining Fe3O4@SiO2NPs；
Fe3O4@SiO2NPs with 466mg ZrCl4Dispersing in DMF, dissolving 2-amino terephthalic acid in the other part of DMF, mixing uniformly by ultrasonic, heating for reaction for 6h, washing the nano material with DMF and methanol in turn, standing with methanol, soaking for activation, and drying in vacuum to obtain Fe3O4@Si02@UiO-66-NH2NPs；
Sodium phytate and CH3COOH solution was mixed and Fe was added3O4@SiO2@UiO-66-NH2NPs, adjusting the pH value of a reaction system, reacting, cooling, washing to be neutral by water, and drying to obtain the composite material I.
4. The functionalized magnetic MOF composite nanomaterial I of claim 3, prepared by the following method:
2.70g FeCl3·6H2O，7.71g CH3COONH40.80g of sodium citrate is mixed and then added into 140mL of glycol, the mixture is ultrasonically dispersed into a uniform phase, the uniform phase is transferred into a Teflon-lined reaction kettle, the reaction is carried out for 16h at 200 ℃, the reaction product is cooled to room temperature, washed for 3 times by ultrapure water, washed for 3 times by absolute ethyl alcohol and dried in vacuum at 40 ℃ to obtain Fe3O4NPs；
300mg Fe3O4NPs are ultrasonically dispersed in 12mL of ultrapure water, 0.75mL (30%, v/v) of ammonia water and 46mL of ethanol are mixed and then added into a reaction system, the ultrasonic dispersion is uniform, 0.9mL of TEOS is diluted in 3mL of ethanol and slowly dripped into the reaction system, the mixture is vigorously stirred at room temperature (25 ℃) for 12 hours, the ultrapure water is washed to be neutral, the absolute ethanol is washed for 3 times, and the mixture is dried in vacuum at 50 ℃ to obtain Fe3O4@SiO2NPs；
200mg Fe3O4@SiO2NPs with 466mg ZrCl4Uniformly dispersing in 30mL of DMF by ultrasonic, dissolving 362mg of 2-amino terephthalic acid in another 30mL of DMF, uniformly mixing the reaction system by ultrasonic, reacting at 120 ℃ for 6h, naturally cooling to room temperature, washing with DMF for 3 times, washing with anhydrous methanol for 3 times, standing with anhydrous methanol to soak the activated material, changing the solution once every 8h, activating for 3d, and vacuum drying at 40 ℃ to obtain Fe3O4@SiO2@UiO-66-NH2NPs；
15mg sodium phytate dissolved in 4mL ultrapure water and 20mL 2% (v/v) CH3COOH solution mixed, 40mg Fe3O4@SiO2@UiO-66-NH2And (3) adding NPs into the system, performing ultrasonic dispersion uniformly, adjusting the pH value of the reaction system to 5, reacting at 50 ℃ for 30min, heating to 115 ℃ for continuous reaction for 12h, naturally cooling to room temperature, washing with ultrapure water to be neutral, and performing vacuum drying at 40 ℃ to obtain the composite material I.
5. The functionalized magnetic MOF composite nanomaterial I of claims 1-2, whose desorbing eluent is selected from the group consisting of: h2SO4HCl and HNO3One of (1) and (b).
6. The functionalized magnetic MOF composite nanomaterial I of claim 5, wherein the desorption eluent thereof is selected from the group consisting of: h2SO4。
7. The functionalized magnetic MOF composite nanomaterial I of claim 6, wherein the desorption eluent thereof is selected from the group consisting of: 0.01MH2SO4。
8. Use of the functionalized magnetic MOF composite nanomaterial of claims 1-2 in radioactive wastewater treatment.
9. Use of the functionalized magnetic MOF composite nanomaterial of claims 1-2 for the adsorption of uranium.
CN202010451860.2A 2020-04-07 2020-05-25 Functionalized magnetic MOF composite nano material, preparation thereof and nuclear industrial application thereof Active CN111375386B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010267097 2020-04-07
CN2020102670978 2020-04-07

Publications (2)

Publication Number Publication Date
CN111375386A true CN111375386A (en) 2020-07-07
CN111375386B CN111375386B (en) 2022-12-13

Family

ID=71220397

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010451860.2A Active CN111375386B (en) 2020-04-07 2020-05-25 Functionalized magnetic MOF composite nano material, preparation thereof and nuclear industrial application thereof

Country Status (1)

Country Link
CN (1) CN111375386B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113075313A (en) * 2021-03-22 2021-07-06 武汉海关技术中心 Method for measuring quinolone drugs in environmental water and fish
CN113457630A (en) * 2021-05-17 2021-10-01 北京化工大学 Preparation method of magnetic amphiphilic metal organic framework material for enriching glycopeptides
CN113698775A (en) * 2021-08-25 2021-11-26 中国地质大学（武汉） P/N/Si multi-element synergetic integrated nano flame retardant and preparation method and application thereof
CN113877549A (en) * 2021-08-17 2022-01-04 福州大学 Selective composite microsphere adsorption material and preparation method and application thereof
CN114797782A (en) * 2021-10-29 2022-07-29 天津大学 Magnetic graphene oxide-metal organic framework nano composite material and preparation method and application thereof
CN115254068A (en) * 2022-05-30 2022-11-01 西北农林科技大学 Magnetic nano-grade bacteria-catching agent containing phytic acid as well as preparation method and application thereof
CN116870877A (en) * 2023-07-04 2023-10-13 河南工业大学 Mixed mode chromatographic stationary phase with multistage pore structure and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105023625A (en) * 2015-06-10 2015-11-04 北京大学 Recovery method for trace of uranium and/or plutonium in radioactive organic liquid waste
CN105148852A (en) * 2015-10-12 2015-12-16 武汉大学 Thiohydroxy-modified magnetic MOFs adsorbent and preparation method and application thereof
CN105688828A (en) * 2016-02-05 2016-06-22 南华大学 Method for preparing plant-inorganic composite adsorbents from phosphoric-acid-modified folium cycas for extracting uranium from seawater
US20170225967A1 (en) * 2016-02-08 2017-08-10 Savannah River Nuclear Solutions, Llc Use of Magnetic Mesoporous Silica Nanoparticles For Removing Uranium From Media
CN107570116A (en) * 2017-09-27 2018-01-12 浙江海洋大学 The magnetic MOFs sorbing materials of antibiotic in a kind of adsorbed water body
CN110586052A (en) * 2019-09-25 2019-12-20 南开大学 Preparation and application of magnetic composite porous network adsorption material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105023625A (en) * 2015-06-10 2015-11-04 北京大学 Recovery method for trace of uranium and/or plutonium in radioactive organic liquid waste
CN105148852A (en) * 2015-10-12 2015-12-16 武汉大学 Thiohydroxy-modified magnetic MOFs adsorbent and preparation method and application thereof
CN105688828A (en) * 2016-02-05 2016-06-22 南华大学 Method for preparing plant-inorganic composite adsorbents from phosphoric-acid-modified folium cycas for extracting uranium from seawater
US20170225967A1 (en) * 2016-02-08 2017-08-10 Savannah River Nuclear Solutions, Llc Use of Magnetic Mesoporous Silica Nanoparticles For Removing Uranium From Media
CN107570116A (en) * 2017-09-27 2018-01-12 浙江海洋大学 The magnetic MOFs sorbing materials of antibiotic in a kind of adsorbed water body
CN110586052A (en) * 2019-09-25 2019-12-20 南开大学 Preparation and application of magnetic composite porous network adsorption material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PEIPEI YANG ET AL.: "Highly efficient immobilization of uranium(VI) from aqueous solution by phosphonate-functionalized dendritic fibrous nanosilica (DFNS)", 《JOURNAL OF HAZARDOUS MATERIALS》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113075313A (en) * 2021-03-22 2021-07-06 武汉海关技术中心 Method for measuring quinolone drugs in environmental water and fish
CN113075313B (en) * 2021-03-22 2022-09-30 武汉海关技术中心 Method for measuring quinolone drugs in environmental water and fish
CN113457630A (en) * 2021-05-17 2021-10-01 北京化工大学 Preparation method of magnetic amphiphilic metal organic framework material for enriching glycopeptides
CN113457630B (en) * 2021-05-17 2023-08-29 北京化工大学 Preparation method of magnetic amphiphilic metal organic framework material for enriching glycopeptides
CN113877549A (en) * 2021-08-17 2022-01-04 福州大学 Selective composite microsphere adsorption material and preparation method and application thereof
CN113698775A (en) * 2021-08-25 2021-11-26 中国地质大学（武汉） P/N/Si multi-element synergetic integrated nano flame retardant and preparation method and application thereof
CN114797782A (en) * 2021-10-29 2022-07-29 天津大学 Magnetic graphene oxide-metal organic framework nano composite material and preparation method and application thereof
CN115254068A (en) * 2022-05-30 2022-11-01 西北农林科技大学 Magnetic nano-grade bacteria-catching agent containing phytic acid as well as preparation method and application thereof
CN115254068B (en) * 2022-05-30 2024-01-26 西北农林科技大学 Magnetic nanometer bacterial catching agent containing phytic acid and preparation method and application thereof
CN116870877A (en) * 2023-07-04 2023-10-13 河南工业大学 Mixed mode chromatographic stationary phase with multistage pore structure and preparation method and application thereof

Also Published As

Publication number Publication date
CN111375386B (en) 2022-12-13

Similar Documents

Publication Publication Date Title
CN111375386B (en) Functionalized magnetic MOF composite nano material, preparation thereof and nuclear industrial application thereof
Zhong et al. Highly efficient enrichment mechanism of U (VI) and Eu (III) by covalent organic frameworks with intramolecular hydrogen-bonding from solutions
Wang et al. Functional group-rich hyperbranched magnetic material for simultaneous efficient removal of heavy metal ions from aqueous solution
Xu et al. 2D water-stable zinc-benzimidazole framework nanosheets for ultrafast and selective removal of heavy metals
Zhao et al. EDTA functionalized Fe3O4/graphene oxide for efficient removal of U (VI) from aqueous solutions
Liu et al. Synthesis of magnetic orderly mesoporous α-Fe2O3 nanocluster derived from MIL-100 (Fe) for rapid and efficient arsenic (III, V) removal
Chen et al. Efficient sorption and reduction of U (VI) on zero-valent iron-polyaniline-graphene aerogel ternary composite
Huo et al. Selective adsorption of cesium (I) from water by Prussian blue analogues anchored on 3D reduced graphene oxide aerogel
Duan et al. Highly enhanced adsorption performance of U (VI) by non-thermal plasma modified magnetic Fe3O4 nanoparticles
Liu et al. Effective adsorption and immobilization of Cr (VI) and U (VI) from aqueous solution by magnetic amine-functionalized SBA-15
Chen et al. Simple hydrothermal synthesis of magnetic MnFe2O4-sludge biochar composites for removal of aqueous Pb2+
Shao et al. Facile fabrication of magnetic cucurbit [6] uril/graphene oxide composite and application for uranium removal
Zhou et al. rGO/CNQDs/ZIF-67 composite aerogel for efficient extraction of uranium in wastewater
Kumar et al. Synthesis of magnetically separable and recyclable magnetic nanoparticles decorated with β-cyclodextrin functionalized graphene oxide an excellent adsorption of As (V)/(III)
Liang et al. Synthesis of a novel three-dimensional porous carbon material and its highly selective Cr (VI) removal in wastewater
Ahmed et al. Phosphate removal from river water using a highly efficient magnetically recyclable Fe3O4/La (OH) 3 nanocomposite
Duan et al. Effect of Fe3O4@ PDA morphology on the U (VI) entrapment from aqueous solution
Hao et al. Highly efficient adsorption and removal of Chrysoidine Y from aqueous solution by magnetic graphene oxide nanocomposite
Li et al. Adsorption properties of pyrene-functionalized nano-Fe3O4 mesoporous materials for uranium
Huang et al. Enhanced surface hydroxyl groups by using hydrogen peroxide on hollow tubular alumina for removing fluoride
Al-Harahsheh et al. High-stability polyamine/amide-functionalized magnetic nanoparticles for enhanced extraction of uranium from aqueous solutions
Jin et al. Removal of Cu (II) ions from aqueous solution by magnetic chitosan-tripolyphosphate modified silica-coated adsorbent: characterization and mechanisms
Liu et al. Synthesis of magnetic polyaniline/graphene oxide composites and their application in the efficient removal of Cu (II) from aqueous solutions
Rani et al. Significance of MOF adsorbents in uranium remediation from water
Gupta et al. 2D and 3D carbon-based adsorbents for an efficient removal of HgII ions: A review

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