CN111375386B - 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 PDFInfo
- Publication number
- CN111375386B CN111375386B CN202010451860.2A CN202010451860A CN111375386B CN 111375386 B CN111375386 B CN 111375386B CN 202010451860 A CN202010451860 A CN 202010451860A CN 111375386 B CN111375386 B CN 111375386B
- Authority
- CN
- China
- Prior art keywords
- sio
- uio
- nps
- adsorption
- washing
- 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.)
- Active
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
Abstract
The invention prepares a novel phytic acid functionalized magnetic MOF composite nano material I (Fe) 3 O 4 @SiO 2 @ 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
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, and the environment is protectedThe structure optimization and 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 used 2 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 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 functionalized magnetic MOF material in the removal of radioactive nuclides in the nuclear waste liquid has important significance for the sustainable development of nuclear energy.
Currently, methods for radioactive wastewater treatment include coagulation precipitation, evaporative concentration, membrane separation, ion exchange, biological, adsorption, 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), a new class of porous materials, are composed of Metal ions or clusters of Metal ions bridged with 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. Wherein the content of the first and second substances,three MOFs Materials, namely ZIFs (Zeolite Imidazolate frameworks), MILs (Materials of Institute Lavoisier) and UiOs (University of Oslo), have the advantages of no collapse of the framework structure in water and good 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-NH 2 The adsorption capacity for U (VI) in the water body is 109.9 and 114.9mg/g. The adsorption capacity of the ammoxim-modified UiO-66-AO for U (VI) was 227.8mg/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, has resulted in the UiO-66 series of materials still being in its infancy 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 Fe 3 O 4 @ZIF-8、Fe 3 O 4 The @ AMCA-MIL-53 composite material can quickly and effectively remove U (VI) in the water body. The magnetic nano composite material has the advantages of large surface area, small particle size, superparamagnetism, no toxicity, mild preparation conditions, low price and the like, can be recycled under an external magnetic field, and solves the problem that the traditional adsorbing material is difficult to separate. However, the adsorption capacity, selectivity and other adsorption properties of the magnetic composite material are still to be further improved. Post-modification of the assembled UiO-66-AO with an ammoxim group enables a rapid and efficient removal of 99% U (VI) in seawater containing U500ppb within 10 min. Magnetic UiO-66 series composite materials (e.g. Fe) 3 O 4 @SiO 2 @Zr-MOF、Fe 3 O 4 @ UiO-66) has been applied to the field of research on removal of pollutants in water bodies, but few literature reports exist on radioactive wastewater treatment. How to combine the UiO-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 magnetismThe preparation method of the radionuclide adsorption material has certain innovation and practical application value.
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 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 elucidated. 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 of metal organic Framework compound (English name Metalloorganic Framework); NPs are short for Nanoparticles (nanoparticules).
Disclosure of Invention
The invention prepares a novel functionalized magnetic MOF composite material (Fe) 3 O 4 @SiO 2 @ UiO-66-PANPs) and a series of evaluations are carried out on the performance of the catalyst in removing U (VI) in a water body, and the TEM characterization of the catalyst is shown in the attached figure 2 of the specification.
The invention discloses a composite material I, and a preparation process thereof is shown in an attached figure 17 in the specification.
The invention also discloses a preparation method of the composite material I, which comprises the following steps:
FeCl 3 ·6H 2 O、CH 3 COONH 4 Mixing sodium citrate with ethylene glycol, ultrasonic dispersing to obtain homogeneous phase, transferring to Teflon-lined reactor for reaction, cooling, washing with water and ethanol, and vacuum drying to obtain F e 3O 4 NPs；
Fe 3 O 4 NPs 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 Fe 3 O 4 @SiO 2 NPs；
Fe 3 O 4 @SiO 2 NPs with 466mg ZrCl 4 Dispersing 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 Fe 3 O 4 @SiO 2 @UiO-66-NH 2 NPs；
Sodium phytate and CH 3 COOH solution was mixed and Fe was added 3 O 4 @SiO 2 @UiO-66-NH 2 NPs, adjusting the pH value of a reaction system, reacting, cooling, washing to be neutral, and drying to obtain Fe 3 O 4 @SiO 2 @ 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 Fe 3 O 4 @SiO 2 @UiO-66-NH 2 TEM and EDX images of (a);
FIG. 2 is Fe 3 O 4 @SiO 2 TEM and EDX images of @ UiO-66-PA;
FIG. 3 is Fe 3 O 4 @SiO 2 TEM and EDX patterns after U (VI) adsorption of @ UiO-66-PA;
FIG. 4 is Fe 3 O 4 @SiO 2 (a)，Fe 3 O 4 @SiO 2 @UiO-66-NH 2 (b) And Fe 3 O 4 @SiO 2 FT-IR plot of @ UiO-66-PA (c);
FIG. 5 shows Fe 3 O 4 @SiO 2 N of @ UiO-66-PA 2 Adsorption and desorption isotherm curveA drawing;
FIG. 6 shows Fe 3 O 4 @SiO 2 A VSM plot of @ UiO-66-PA;
FIG. 7 shows Fe at different pH values 3 O 4 @SiO 2 @UiO-66-NH 2 (a) And Fe 3 O 4 @SiO 2 Zeta potential value diagram of @ UiO-66-PA (b);
FIG. 8 shows Fe in different U (VI) initial solutions 3 O 4 @SiO 2 @UiO-66-NH 2 (a) And Fe 3 O 4 @SiO 2 The @ UiO-66-PA (b) adsorption capacity map;
FIG. 9 shows Fe at different adsorption times 3 O 4 @SiO 2 @UiO-66-NH 2 (a) And Fe 3 O 4 @SiO 2 A plot of the adsorption capacity of @ UiO-66-PA (b) for 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 temperatures 3 O 4 @SiO 2 Adsorption isotherm plot of @ UiO-66-PA;
FIG. 13 is a plot of fitted Langmuir and Freundlich adsorption isotherms;
FIG. 14 is the solution ionic strength vs. Fe 3 O 4 @SiO 2 Influence graph of the adsorption capacity of @ UiO-66-PA;
FIG. 15 shows Fe 3 O 4 @SiO 2 The adsorption selectivity profile of @ UiO-66-PA for U (VI);
FIG. 16 is Fe 3 O 4 @SiO 2 Graph of desorption effect of @ UiO-66-PA;
FIG. 17 is a schematic diagram of the preparation process of composite I of the present invention.
Examples
Example 1 Fe 3 O 4 @SiO 2 @UiO-66-PA NP s Preparation of (2)
1、Fe 3 O 4 Preparation of NPs
2.70g FeCl 3 ·6H 2 O，7.71g CH 3 COONH 4 0.80g of sodium citrate is mixed and 140mL of ethyl acetate is addedUltrasonically dispersing into uniform phase in diol, transferring into Teflon-lined reaction kettle, reacting at 200 deg.C for 16h, naturally cooling to room temperature, washing with ultrapure water for 3 times, washing with anhydrous ethanol for 3 times, and vacuum drying at 40 deg.C to obtain Fe 3 O 4 NPs。
2、Fe 3 O 4 @SiO 2 Preparation of NPs
300mg Fe 3 O 4 NPs 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 Fe 3 O 4 @SiO 2 NPs。
3、Fe 3 O 4 @SiO 2 @UiO-66-NH 2 Preparation of NPs
200mg Fe 3 O 4 @SiO 2 NPs with 466mg ZrCl 4 Uniformly dispersing in 30mL of DMF by ultrasonic, dissolving 362mg of 2-aminoterephthalic 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 drying at 40 ℃ in vacuum to obtain Fe 3 O 4 @SiO 2 @UiO-66-NH 2 NPs。
4、Fe 3 O 4 @SiO 2 Preparation of @ UiO-66-PA NPs
15mg of sodium phytate was dissolved in 4mL of ultrapure water and 20mL of 2% (v/v) CH 3 COOH solution mixed, 40mg Fe 3 O 4 @SiO 2 @UiO-66-NH 2 NPs 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 Fe 3 O 4 @SiO 2 @ 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 1 3 O 4 @SiO 2 @UiO-66-NH 2 ，Fe 3 O 4 @SiO 2 @ UiO-66-PA for adsorption of U (VI) Fe 3 O 4 @SiO 2 The @ UiO-66-PA was subjected to TEM and EDX characterization 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 seen 3 O 4 @SiO 2 The diameter of the NPs is 240-300nm, and 40nm SiO exists on the outer layer 2 Layer of SiO 2 Coated with 50nm thick UiO-66-NH 2 The Zr element is uniformly dispersed on the surface of the nanoparticles.
As can be seen from FIG. 2, the phosphate group is in Fe after phytic acid modification 3 O 4 @SiO 2 @UiO-66-NH 2 The NPs surface was successfully modified. Meanwhile, the silicon layer is partially dissolved, but the nano structure of the iron oxide is not damaged, and some silicon-containing particles permeate into MOF mesopores, and the mesopore structure is favorable for adsorption of the nano composite material.
From FIG. 3, fe can be seen 3 O 4 @SiO 2 After 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 Fe 3 O 4 @SiO 2 The @ 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 1 3 O 4 @SiO 2 ，Fe 3 O 4 @SiO 2 @UiO-66-NH 2 And Fe 3 O 4 @SiO 2 @ 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 Fe 3 O 4 @SiO 2 590cm in the spectrum of NPs (a) -1 The peak at (B) is attributed to stretching vibration of Fe-O bond, 1086cm -1 The peak at (A) is derived from stretching vibration of Si-O-Si, and 1628cm -1 At a position of 3431cm -1 Absorption peaks at are respectively corresponding toC = stretching vibration of the O key and stretching vibration of the O-H or N-H key. After modification of the MOF layer, fe 3 O 4 @SiO 2 @UiO-66-NH 2 NPs (b) infrared spectrum shows new absorption peak, 1428cm -1 、1506cm -1 And 1572cm -1 Respectively represents the expansion vibration absorption peaks of C-O, C = C and N-H bonds in the MOF layer. In FIG. c, 1055em -1 The characteristic stretching vibration absorption peak at P = O bond, indicating successful modification of the phosphate group.
Example 4N 2 Characterization by adsorption-desorption
The instrument model is as follows: micromeritics ASAP (USA) 2010Apparatus
Fe of example 1 3 O 4 @SiO 2 @ UiO-66-PA N according to the existing method 2 And (5) performing adsorption-desorption characterization. The results are shown in figure 5 of the specification.
From FIG. 5, fe can be seen 3 O 4 @SiO 2 The isotherm of @ UiO-66-PANPs is type IV, indicating a mesoporous structure. Using Brunauer-Emmett-Teller (BET) method in terms of N 2 The specific surface area, the total pore volume and the pore diameter of the adsorbing material are respectively 182.8m by the adsorption isotherm calculation 2 /g，0.149cm 3 G 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 1 3 O 4 @SiO 2 The 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 seen 3 O 4 @SiO 2 @ UiO-66-PA NPs are paramagnetic, saturated magnetizations (M) s ) The value was 53.19emu g -1 Description of Fe 3 O 4 @SiO 2 @ 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 1 3 O 4 @SiO 2 @UiO-66-NH 2 And Fe 3 O 4 @SiO 2 The 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 seen 3 O 4 @SiO 2 @UiO-66-NH 2 The surface charge of NPs does not change significantly over a large pH range (1.5-5.5), while Fe 3 O 4 @SiO 2 @ UiO-66-PANPs have a large change in surface charge due to surface modification of phosphate groups. Fe 3 O 4 @SiO 2 @ 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 =5.0 3 O 4 @SiO 2 The Zeta potential of @ UiO-66-PANPs is-17.6 mV. Fe 3 O 4 @SiO 2 The higher electronegativity of the surface of the @ UiO-66-PANPs is favorable for avoiding agglomeration among nano particles and contributes to the UO 2 (OH) + The plasma rapidly moves to the surface of the material, 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 1 3 O 4 @SiO 2 @UiO-66-NH 2 And Fe 3 O 4 @SiO 2 @ 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 seen 3 O 4 @SiO 2 The adsorption capacity of @ UiO-66-PA NPs (b) for U (VI) increases rapidly with increasing pH, fe at pH =5.0 3 O 4 @SiO 2 The adsorption quantity of the @ UiO-66-PANPS to the U (VI) reaches the maximum value of 249.5mg/g (q) e ). At the same time, fe 3 O 4 @SiO 2 @UiO-66-NH 2 The 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 1 3 O 4 @SiO 2 @UiO-66-NH 2 And Fe 3 O 4 @SiO 2 @ 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 15min 3 O 4 @SiO 2 The adsorption of U (VI) by the @ UiO-66-PA NPs (b) reaches equilibrium rapidly, which is attributed to Fe 3 O 4 @SiO 2 The strong complexation between the phosphate groups on the surface of @ UiO-66-PA NPs and U (VI).
Example 9 Effect of initial concentration of U (VI) on adsorption Capacity
The instrument model is as follows: UV-2600 (A) ultraviolet visible spectrophotometer
Fe of example 1 3 O 4 @SiO 2 @ UiO-66-PA the adsorption capacity was determined at different initial U (VI) concentrations. The results are shown in figure 12 of the specification.
As can be seen from FIG. 12, as the initial concentration of U (VI) was gradually increased from 20mg/L, the amount of adsorption also significantly increased. Fe at an initial concentration of U (VI) of 200mg/L 3 O 4 @SiO 2 The 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 1 3 O 4 @SiO 2 @ 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.
Table 1: adsorption effect of different nano adsorption materials
It can be seen from FIG. 12 that as the temperature increases, fe 3 O 4 @SiO 2 The increased U (VI) adsorption of @ UiO-66-PANPs is attributed to Fe 3 O 4 @SiO 2 The adsorption thermodynamics of @ UiO-66-PANPs on U (VI) is a spontaneous endothermic process. At the same time, fe 3 O 4 @SiO 2 The phosphate group grafted with the @ UiO-66-PANPS enables the adsorbent to have higher adsorption capacity (320.3 mg/g) and adsorption rate (15 min). As can be seen from Table 1, fe 3 O 4 @SiO 2 The 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 nano materials at different reaction temperatures and component proportions, and carrying out condition screening and proportion optimization. The results are shown in Table 2.
Table 2: fe 3 O 4 @SiO 2 Screening 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 U (VI) by the material 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 material structure is damaged as the reaction system is strengthened by the high content of sodium phytate.
Example 12 Material adsorption kinetic 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.
Table 3: fe 3 O 4 @SiO 2 Kinetic 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 model e The cal (244.50 mg/g) value is close to q e，exp (245.79 mg/g) further elucidating that the adsorption process follows a pseudo-second order model, indicating that uranium is in Fe 3 O 4 @SiO 2 Adsorption 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 function 0 (entropy change), Δ H 0 (enthalpy Change) and Δ G 0 (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.
Table 4: adsorption constants of Langmuir and Freundlich
Table 5: thermodynamic parameters of adsorption
As can be seen from FIGS. 13 and Table 4, R is a group 2 The value is higher, the adsorption process follows a Langmuir isotherm model, and U (VI) is shown in Fe 3 O 4 @SiO 2 Adsorption on @ UiO-66-PA NPs is a monolayer surface complexation process. As can be seen from Table 5, a positive Δ H 0 The values prove that U (VI) is in Fe 3 O 4 @SiO 2 Adsorption on @ UiO-66-PANPS is endothermic, positive Δ S 0 Indicating that the randomness of the solid-liquid interface increases during the adsorption process, positive Δ G 0 Indicating that the adsorption process is spontaneous, fe 3 O 4 @SiO 2 @ UiO-66-PANPs have a high affinity for U (VI) in aqueous solution. Δ G 0 The values decrease with increasing temperature, indicating that the higher the temperature, the U (VI) is in Fe 3 O 4 @SiO 2 The 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 1 3 O 4 @SiO 2 @ 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: elelement 2 high-resolution inductively coupled plasma mass spectrometer
Fe of example 1 3 O 4 @SiO 2 @ UiO-66-PA for adsorptive selectivity characterization under conditions containing competing ions. The results are shown in figure 15 of the specification.
As can be seen from FIG. 15, fe 3 O 4 @SiO 2 The adsorption capacity of the @ UiO-66-PANPs to U (VI) is obviously higher than that of other coexisting metal ions. Fe 3 O 4 @SiO 2 Selective S for uranium by @ UiO-66-PANPS u The value was 82.3%, indicating good selectivity to U (VI). Fe 3 O 4 @SiO 2 The 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 water 3 O 4 @SiO 2 The adsorption selectivity of the @ UiO-66-PA NPs to U (VI) is still better.
Example 16 evaluation of Material Desorption conditions
The instrument model is as follows: UV-2600 (A) ultraviolet visible spectrophotometer
Fe of example 1 3 O 4 @SiO 2 Characterization of desorption Performance by selecting appropriate eluent from uranium-loaded Fe @ UiO-66-PA 3 O 4 @SiO 2 Desorption of uranium in @ UiO-66-PA provides better recovery of U (VI). The results are shown in FIG. 16 of the specification.
As can be seen from FIG. 16, different 0.01M acidic solutions (H) were used 2 SO 4 HCl and HNO 3 ) Fe loaded with U (VI) was analyzed 3 O 4 @SiO 2 Effect of U (VI) desorption in @ UiO-66-PA, H 2 SO 4 HCl and HNO 3 The desorption rates of (a) were 94.21, 81.50 and 25.36%, respectively. The results show that: 0.01M H 2 SO 4 The solution is more suitable for desorption of U (VI) from the material.
Claims (5)
1. The application of the functionalized magnetic MOF composite nano material in uranium adsorption is characterized in that the functionalized magnetic MOF composite nano material is Fe 3 O 4 @SiO 2 @ UiO-66-PA, its preparation method is as follows:
FeCl is added 3 ·6H 2 O、CH 3 COONH 4 Mixing 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 Fe 3 O 4 NPs；
Fe 3 O 4 NPs 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 Fe 3 O 4 @SiO 2 NPs；
Fe 3 O 4 @SiO 2 NPs with 466mg ZrCl 4 Dispersing in DMF, dissolving 2-amino terephthalic acid in the other part of DMF, uniformly mixing by ultrasonic, heating for reaction for 6 hours, washing the nano material by using DMF and methanol in turn, standing, soaking and activating by using methanol, and drying in vacuum to obtain Fe 3 O 4 @SiO 2 @UiO-66-NH 2 NPs；
Sodium phytate and CH 3 COOH solution was mixed and Fe was added 3 O 4 @SiO 2 @UiO-66-NH 2 NPs, adjusting the pH value of a reaction system, reacting, cooling, washing to be neutral, and drying to obtain Fe 3 O 4 @SiO 2 @UiO-66-PA。
2. The use according to claim 1, wherein the functionalized magnetic MOF composite nanomaterial is prepared by the following method:
2.70g FeCl 3 ·6H 2 O，7.71g CH 3 COONH 4 0.80g 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 Fe 3 O 4 NPs；
300mg Fe 3 O 4 NPs are ultrasonically dispersed in 12mL of ultrapure water, 0.75mL of ammonia water with the concentration of 30 percent v/v 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 of 25 ℃ for 12 hours, the ultrapure water is washed to be neutral, the absolute ethanol is washed for 3 times, and the vacuum drying is carried out at 50 ℃ to obtain Fe 3 O 4 @SiO 2 NPs；
200mg Fe 3 O 4 @SiO 2 NPs with 466mg ZrCl 4 Uniformly dispersing in 30mL of DMF by ultrasonic, dissolving 362mg of 2-aminoterephthalic 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 drying at 40 ℃ in vacuum to obtain Fe 3 O 4 @SiO 2 @UiO-66-NH 2 NPs；
15mg sodium phytate dissolved in 4mL ultrapure water with a concentration of 20mL CH of 2% 3 COOH solution mixed, 40mg Fe 3 O 4 @SiO 2 @UiO-66-NH 2 NPsAdding 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 ℃, continuing to react for 12h, naturally cooling to room temperature, washing with ultrapure water to neutrality, and drying at 40 ℃ in vacuum to obtain Fe 3 O 4 @SiO 2 @UiO-66-PA。
3. Use according to any one of claims 1-2, characterized in that the desorbing eluent is selected from the group consisting of H 2 SO 4 HCl or HNO 3 One kind of (1).
4. Use according to claim 3, characterized in that the desorbing eluent is selected from H 2 SO 4 。
5. Use according to claim 4, characterized in that the desorbing eluent is selected from 0.01M H 2 SO 4 。
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 CN111375386A (en) | 2020-07-07 |
| CN111375386B true 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) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN113698775B (en) * | 2021-08-25 | 2022-04-22 | 中国地质大学（武汉） | P/N/Si multi-element synergetic integrated nano flame retardant and preparation method and application thereof |
| CN114797782B (en) * | 2021-10-29 | 2023-06-16 | 天津大学 | Magnetic graphene oxide-metal organic framework nanocomposite and 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 |
Citations (5)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170225967A1 (en) * | 2016-02-08 | 2017-08-10 | Savannah River Nuclear Solutions, Llc | Use of Magnetic Mesoporous Silica Nanoparticles For Removing Uranium From Media |
-
2020
- 2020-05-25 CN CN202010451860.2A patent/CN111375386B/en active Active
Patent Citations (5)
| 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 |
| 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)
| Title |
|---|
| Highly efficient immobilization of uranium(VI) from aqueous solution by phosphonate-functionalized dendritic fibrous nanosilica (DFNS);Peipei Yang et al.;《Journal of Hazardous Materials》;20180927;第363卷;第248-257页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111375386A (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111375386B (en) | Functionalized magnetic MOF composite nano material, preparation thereof and nuclear industrial application thereof | |
| Alqadami et al. | Adsorptive performance of MOF nanocomposite for methylene blue and malachite green dyes: kinetics, isotherm and mechanism | |
| 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 | |
| Liu et al. | In situ preparation of chitosan/ZIF-8 composite beads for highly efficient removal of U (VI) | |
| Yuan et al. | Glycine derivative-functionalized metal-organic framework (MOF) materials for Co (II) removal from aqueous solution | |
| Huo et al. | Selective adsorption of cesium (I) from water by Prussian blue analogues anchored on 3D reduced graphene oxide aerogel | |
| 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 | |
| Xie et al. | Porous NiFe-oxide nanocubes derived from prussian blue analogue as efficient adsorbents for the removal of toxic metal ions and organic dyes | |
| Liang et al. | Synthesis of a novel three-dimensional porous carbon material and its highly selective Cr (VI) removal in wastewater | |
| Ntim et al. | Adsorption of arsenic on multiwall carbon nanotube–zirconia nanohybrid for potential drinking water purification | |
| Fan et al. | Preparation of magnetic modified chitosan and adsorption of Zn2+ from aqueous solutions | |
| Chen et al. | Simple hydrothermal synthesis of magnetic MnFe2O4-sludge biochar composites for removal of aqueous Pb2+ | |
| 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 | |
| Qu et al. | UiO-66 (Zr)-derived t-zirconia with abundant lattice defect for remarkably enhanced arsenic removal | |
| Hao et al. | Highly efficient adsorption and removal of Chrysoidine Y from aqueous solution by magnetic graphene oxide nanocomposite | |
| 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 | |
| Wang et al. | Preparation of copper based metal organic framework materials and its effective adsorptive removal of ceftazidime from aqueous solutions | |
| Su et al. | Fabrication of lanthanum-modified MOF-808 for phosphate and arsenic (V) removal from wastewater | |
| Mohammadi et al. | Synthesis and characterization of NH 2-SiO 2@ Cu-MOF as a high-performance adsorbent for Pb ion removal from water environment | |
| Cheng et al. | Enhanced adsorption performance of UiO-66 via modification with functional groups and integration into hydrogels |
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 |