CN111266091A - Carboxyl modified graphene oxide @ metal organic framework composite material and preparation method and application thereof - Google Patents
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Abstract
The invention relates to the technical field of environment and chemical industry, in particular to a carboxyl modified graphene oxide @ metal organic framework composite material and a preparation method and application thereof. The composite material is prepared by reacting chloroacetic acid modified graphene oxide GO-COOH-X with metal organic framework UIO-66-NH2Compounding, wherein X represents GO-COOH in the mass percentage of the composite material, and X is 9, 17, 23, 33, 44 or 50 percent. The invention relates to a method for synthesizing an adsorbent by taking a metal organic framework as a matrix and taking carboxyl modified graphene oxide as an adsorption functional group. The adsorbent has the advantages of simple preparation method, strong regeneration capacity, good stability, high adsorption capacity to Nd (III), and maximum adsorption capacity of 146mg g‑1Wide application range and practical applicability.
Description
Technical Field
The invention relates to the technical field of environment and chemical industry, in particular to a carboxyl modified graphene oxide @ metal organic framework composite material and a preparation method and application thereof.
Background
Rare Earth (Rare Earth) is a short name for Rare Earth elements, and is a general name for seventeen metal elements in the third subgroup (lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium) of the chemical periodic table and elements (scandium and yttrium) having similar properties to the elements. According to the difference of the electron shell structure and the physicochemical properties of rare earth elements, rare earth elements are classified into: light rare earths (lanthanum, cerium, praseodymium, neodymium, promethium), medium rare earths (samarium, europium, gadolinium, terbium, dysprosium) and heavy rare earths (holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium). The rare earth elements mainly exist in the crust of the earth in the form of bastnaesite, monazite, xenotime and other rare earth ores. The 4f electron sublayer of rare earth elements is very unique in structure, rich in transition energy level, and as the atomic number increases, the radius of rare earth ions (except for y (iii)) tends to decrease, which are all properties which are rare to other metals. Due to these irreplaceable physical and chemical properties, rare earth elements are widely used in the fields of catalysis, gas storage, industrial metallurgy, optical materials, and the like, and are regarded as industrial vitamins. Along with the progress of science and technology and the continuous breakthrough of application technology, the value of rare earth elements is higher and higher, the rare earth elements become support materials of various fields such as national civilians and national security, and even rare earth resources are regarded as extremely important strategic resources by many countries, so that the importance of the rare earth resources can be seen.
At present, methods for recovering rare earth elements mainly include chemical precipitation methods, solvent extraction methods, liquid-membrane separation methods and adsorption methods. However, most of the above methods have significant disadvantages such as high operation cost, poor selectivity, environmental pollution caused by organic waste liquid, and low recovery rate of particularly low concentration rare earth solution.
The MOFs is a three-dimensional network crystal material formed by self-assembling metal cations, oxygen-nitrogen-containing polydentate aromatic carboxylic acid and alkali organic ligands. Compared with the traditional porous materials (zeolite, molecular sieve, activated carbon and the like), the MOFs material has high porosity and specific surface, and the size of an internal pore channel can be regulated and controlled by changing the length of an organic ligand. In particular, in order to make the MOFs material have unique chemical properties, various functional groups are introduced by using a post-modification method or an in-situ synthesis method. Based on these excellent characteristics, the research of MOFs materials has become a hot spot in the field of modern novel porous materials, and has shown potential application value in the fields of adsorption and separation, catalysis, molecular induction and detection, membrane materials and the like. However, the number of functional groups on pure MOFs is limited, and the adsorption capacity for rare earth is relatively low. In order to explore the potential of application of MOFs in rare earth separation, further improvements are necessary. Graphene Oxide (GO) is a novel carbon-based material discovered in the twenty-first century, and is an oxidized derivative of graphite generated under the action of a strong oxidant. GO has a large specific surface area, is stable in chemical properties in water, contains rich oxygen-containing groups on the surface, and is considered to be a good adsorption matrix material. Graphene oxide is easily modified by other functional reagents and is also easily compounded with other materials through various bonding modes, and in recent years, more and more attention has been paid to research on graphene oxide composite materials. The invention provides a composite material combining graphene oxide and a metal organic framework through hydrogen bonds and coordination, and provides a new idea for rare earth recovery.
Disclosure of Invention
The invention aims to provide a carboxyl modified graphene oxide @ metal organic framework composite material, which takes a metal organic framework as a matrix and takes the carboxyl modified graphene oxide as an adsorption functional group to synthesize an adsorbent. The adsorbent has the advantages of simple preparation method, strong regeneration capacity, high adsorption capacity and selectivity to Nd (III), and practical applicability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2The composite material is prepared by mixing chloroacetic acid modified graphene oxide GO-COOH-X and metal organic framework UIO-66-NH2Compounding, wherein X represents GO-COOH in the mass percentage of the composite material, and X is 9, 17, 23, 33, 44 or 50 percent.
The carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2The preparation method comprises the following steps:
1) preparing graphene oxide: mixing and stirring concentrated sulfuric acid, concentrated phosphoric acid and graphite powder in an ice bath for 20min, slowly adding potassium permanganate, slowly heating the solution to 313-333K for reaction for 5-6h, cooling the solution to room temperature, slowly pouring the solution into ice water, stirring, dropwise adding hydrogen peroxide until the color of the solution is changed from yellow to golden yellow, and stopping dropwise adding, wherein the golden material is graphene oxide;
2) synthesizing carboxyl modified graphene oxide: centrifuging graphene oxide, washing with water to neutrality, drying, dissolving graphene oxide in water, performing ultrasonic treatment at room temperature for 1-2h, adding sodium hydroxide and chloroacetic acid, performing ultrasonic dispersion again, adjusting the pH value of the solution to neutrality, washing with water, and drying to obtain a product named as GO-COOH;
3) metal organic framework UIO-66-NH2The synthesis of (2): dissolving zirconium tetrachloride and 2-amino terephthalic acid in N, N-dimethylformamide, adding glacial acetic acid, performing ultrasonic dispersion, putting the ultrasonic solution into a reaction kettle, cooling to room temperature after reaction, putting the product into N, N-dimethylformamide, stirring for 1h, centrifuging, washing with methanol, and performing vacuum drying at 333K to obtain UIO-66-NH2；
4) Synthesizing a carboxyl modified graphene oxide @ metal organic framework composite material: reacting UIO-66-NH2Adding GO-COOH into N, N-dimethylformamide, performing ultrasonic treatment for 20min, stirring the ultrasonic solution at room temperature, centrifuging, and mixing the obtained product with methanolAlcohol and water washing, drying under 323K, putting the dried product into a reaction kettle, adding 30-50mL of water for hydrothermal reaction, and finally centrifugally drying the obtained gray product to obtain the product named as GO-COOH-X @ UIO-66-NH2Wherein X represents GO-COOH in the mass percentage of the composite material, and X is 9, 17, 23, 33, 44 or 50 percent.
Preferably, the carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2In step 1), concentrated sulfuric acid: concentrated phosphoric acid: graphite powder: potassium permanganate 180mL ═ 150-: 10-30 mL: 1.5-2.0 g: 15 g.
Preferably, the carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2And in the step 2), oxidizing the graphene: sodium hydroxide: chloroacetic acid ═ 0.1: 0.1-2: 1-5.
Preferably, the carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2And in the step 3), according to the solid-liquid ratio, zirconium tetrachloride: 2-amino terephthalic acid: n, N-dimethylformamide ═ 0.2 to 0.5 g: 0.1-0.3 g: 100-.
Preferably, the carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2In the step 3), the reaction temperature is 373-393K, and the reaction time is 12-16 h.
Preferably, the carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2And in the step 4), the temperature of the hydrothermal reaction is 343-393K, and the time is 10-15 h.
The carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2The application of the neodymium iron boron adsorbent in the recovery of rare earth metal neodymium is taken as an adsorbent.
Preferably, the above application, method is as follows: adjusting the pH of the solution to 1-7 in a solution containing neodymium, adding the composite material GO-COOH-X @ UIO-66-NH according to claim 12After 12h of adsorption with shaking, elution was carried out with an eluent.
Preferably, in the above application, the eluent is 0.5 mol.L-1Nitric acid of (2).
The invention has the beneficial effects that:
(1) the carboxyl modified graphene oxide @ metal organic framework composite material prepared by the invention has high separation efficiency and good stability as an adsorbent, the adsorption capacity is good in the cycle performance for most times, the application range is wide, and the application range is practical.
(2) The invention has fast adsorption speed and good desorption performance, and the maximum adsorption capacity to Nd (III) can reach 146mg g-1。
(3) The composite material prepared by the invention is used for adsorbing rare earth elements Nd (III). The synthetic process of the adsorbent has the advantages of easy control of conditions, low energy consumption and simple operation, and Nd (III) can be selectively recovered from coexisting ion solutions of Cu (II), Zn (II), Mn (II), Co (II), Al (III) and the like.
Drawings
FIG. 1 is GO-COOH-X @ UIO-66-NH2Schematic synthesis of (a).
FIG. 2 is GO-COOH-44@ UIO-66-NH2FT-IR diagram of (1).
FIG. 3 shows GO, GO-COOH, UIO-66-NH2And GO-COOH-44@ UIO-66-NH2SEM picture of (1); wherein a is GO, b is GO-COOH, c is UIO-66-NH2D is GO-COOH-44@ UIO-66-NH2。
Fig. 4 is an effect of the addition amount of the carboxyl group-modified graphene oxide on nd (iii) adsorption performance.
FIG. 5 is GO-COOH-44@ UIO-66-NH2Adsorption kinetics for adsorption of Nd (III).
FIG. 6 is GO-COOH-44@ UIO-66-NH2Adsorbing light rare earth.
FIG. 7 is the effect of the coexisting ion concentration on the Nd (III) adsorption performance.
FIG. 8 is GO-COOH-44@ UIO-66-NH2And (4) cyclic elution.
FIG. 9 is GO-COOH-44@ UIO-66-NH2Stability of (2).
Detailed Description
For better understanding of the technical solution of the present invention, specific examples are described in further detail, but the solution is not limited thereto.
Example 1 carboxyl-modified graphene oxide @ metal organic framework composite material
(I) carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2Preparation of
The synthesis process is shown in figure 1.
The preparation method comprises the following steps:
1) preparing graphene oxide: mixing 180mL of concentrated sulfuric acid, 20mL of concentrated phosphoric acid and 1.5g of graphite powder in an ice bath, stirring for 20min, slowly adding 15g of potassium permanganate, slowly heating the solution to 323K, reacting for 6h, cooling the solution to room temperature, slowly pouring the solution into ice water, and uniformly stirring. And dropwise adding hydrogen peroxide into the solution until the color of the solution is changed from yellow to golden yellow, and stopping dropwise adding, wherein the golden yellow material is graphene oxide.
2) Synthesizing carboxyl modified graphene oxide: and centrifuging the graphene oxide, washing the graphene oxide to be neutral by using water, and drying the graphene oxide. 0.1g of graphene oxide is weighed and dissolved in 100mL of water, and ultrasonic sound is carried out for 2h at room temperature. Adding 1g of sodium hydroxide and 1.6g of chloroacetic acid into the solution after ultrasonic treatment, performing ultrasonic dispersion again, adjusting the pH of the solution to be neutral, washing with water, and drying to obtain a product named as GO-COOH.
3) Metal organic framework UIO-66-NH2The synthesis of (2): 0.23g of zirconium tetrachloride and 0.1g of 2-aminoterephthalic acid were dissolved in 102mL of N, N-dimethylformamide, and 23mL of glacial acetic acid was added thereto and subjected to ultrasonic dispersion. And (3) putting the solution after ultrasonic treatment into a reaction kettle, reacting for 16 hours at 393K, and cooling to room temperature. Putting the product into N, N-dimethylformamide, stirring for 1h, centrifuging, washing with methanol for 3 times, and vacuum drying at 333K to obtain UIO-66-NH2。
4) Preparing a composite material: respectively adding 0.1g of UIO-66-NH2And 10, 20, 30, 50, 80, 100mg of GO-COOH were added into 30mL of N, N-dimethylformamide and sonicated for 20 min. The sonicated solution was stirred at room temperature, centrifuged, and the product washed 3 times with methanol and water, respectively, and dried at 323K for 12 h. Putting the dried product into a reaction kettle, and adding 30mL in water, the hydrothermal reaction is carried out for 12h at 393K, and finally the obtained grey product is centrifugally dried. Respectively obtain GO-COOH-9@ UIO-66-NH2、GO-COOH-17@UIO-66-NH2、GO-COOH-23@UIO-66-NH2、GO-COOH-33@UIO-66-NH2、GO-COOH-44X@UIO-66-NH2、GO-COOH-50@UIO-66-NH2。
(di) carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2Is characterized by
1) FT-IR analysis: as shown in FIG. 2, compared with the original Graphene Oxide (GO), the chloroacetic acid modified graphene (GO-COOH) is 822cm-1A new peak appears, and the peak is attributed to C-H vibration of chloroacetic acid; 1590cm-1The absorption peak is obviously enhanced compared with GO, and the peak is attributed to chloroacetic acid and C ═ O in GO, which proves that the content of carboxyl in the material is increased, and the graphene oxide is functionalized by chloroacetic acid. In the material UIO-66-NH2In the middle, at 3354 and 1653cm-1The absorption peak is an N-H group, the intensity of the absorption peak is obviously weakened after the absorption peak is compounded with GO-COOH, and after the two materials are compounded, the N-H position is 1653cm from the original position-1Blue shift to 1685cm-1It was demonstrated that N-H is mainly hydrogen bonded to-COOH in GO-COOH, which allows the two materials to be composited together. In summary, GO-COOH and UIO-66-NH2The two materials were successfully compounded together.
2) SEM analysis: GO, GO-COOH, UIO-66-NH2And GO-COOH-44@ UIO-66-NH2SEM of (4). From fig. 3a and 3b, it can be observed that GO is a lamellar structure with more wrinkles. After chloroacetic acid modification, the GO surface is accumulated to a certain degree, but the layered structure of graphene is still kept. From FIG. 3c, it can be seen that UIO-66-NH2Has regular octahedral structure, smooth surface and clear edges and corners. After compounding with GO-COOH, UIO-66-NH2The octahedral structure is not damaged, but the surface of the material becomes rough, the edge angle is not clear, and the octahedral structure is obviously seen in UIO-66-NH2The surface of (2) is attached with the layer of carboxyl modified graphene oxide, which shows that the two materials are successfully compounded.
Example 2 recovery of neodymium from carboxy-modified graphene oxide @ metal organic framework composite material
Effect of addition amount of (mono) carboxyl-modified graphene oxide on Nd (III) adsorption Property
The method comprises the following steps: 5mg of the composite GO-COOH-9@ UIO-66-NH prepared in example 1 were each taken2、GO-COOH-17@UIO-66-NH2、GO-COOH-23@UIO-66-NH2、GO-COOH-33@UIO-66-NH2、GO-COOH-44X@UIO-66-NH2、GO-COOH-50@UIO-66-NH25mL of each of 30 mg. multidot.L was added-1Nd (iii) solution (c), which was shaken in a shaking chamber at 303K for 24 hours, the results are shown in fig. 4. As the addition amount of GO-COOH is increased, the adsorption amount of Nd (III) by the material is also increased. When the addition amount of GO-COOH is 80mg, namely X is 44, the composite material achieves higher adsorption capacity, and the adsorption rate of the material is not obviously changed when the addition amount of GO-COOH is continuously increased. This is because GO-COOH surface contains a large number of carboxyl groups, which are complexed to make UIO-66-NH2The surface of (2) introduces more adsorption sites, thereby increasing adsorption performance.
(II) GO-COOH-44@ UIO-66-NH2Adsorption kinetics for Nd (III)
The method comprises the following steps: respectively taking 30mg and L-15mL of Nd (III) solution, then 5mg of GO-COOH-44@ UIO-66-NH prepared in example 1 was added2The adsorbent was shaken at 303, 313 and 323K for 5min, 10min, 30min, 1h, 3h, 5h, 8h, 12h and 24h, respectively, and the concentration of nd (iii) in the solution was measured, and the results are shown in fig. 5.
As can be seen from fig. 5, at pH 6, the amount of adsorption of nd (iii) by the adsorbent gradually increased with increasing time, and the equilibrium was reached after 3 hours. GO-COOH-44@ UIO-66-NH2The rapid adsorption of Nd (III) is mainly due to the existence of a large number of adsorption functional groups (-COOH, -NH) on the surface of the adsorbent2) So that the adsorption can reach the equilibrium in a short time.
(III) GO-COOH-44@ UIO-66-NH2Adsorption of light rare earths
Weighing 5mg of GO-COOH-44@ UIO-66-NH25mL of 20 mg. L was added-1The pH of the solution is adjusted to be1-6, shaking for 3h at 303K in a shaking box of 180r/min, and obtaining the result shown in FIG. 6. As can be seen from the figure, at pH 3 or more, GO-COOH-44@ UIO-66-NH is present, compared with other light rare earth elements2The adsorption capacity to Nd (III) in the light rare earth solution is strongest.
(IV) Effect of coexisting ion concentration on Nd (III) adsorption Properties
The method comprises the following steps: weighing 10mg of GO-COOH-44@ UIO-66-NH2A mixed solution of 10mLCu (II), Zn (II), Mn (II), Co (II), Al (III) and Nd (III) was added, wherein the ratio of the concentration of coexisting ions to the concentration of Nd (III) was 1:1 and 2:1, respectively, the pH of the solution was adjusted to 6, and the mixture was shaken in a shaking chamber at 303K and 180r/min for 3 hours, as shown in FIG. 7.
As is clear from the graph, even when the concentration of coexisting ions is 2 times that of nd (iii), the adsorption rate of nd (iii) by the adsorbent can be 90% or more. Sel selectivity factor of Nd (III) and other metal ionsNd/XAre listed in table 1. As can be seen from the data in Table 1, all Sel's were observed at a concentration ratio of 1:1 of the coexisting ion concentration to the rare earth element Nd (III)Nd/XValues greater than 1.5, complete separation can be achieved. Thus, GO-COOH-44@ UIO-66-NH can be seen2Has great potential for the selective separation of rare earth elements Nd (III).
TABLE 1 separation coefficient of Nd (III) from other coexisting metal ions
(V) elution effects of different eluents on Nd (III)
100mg of GO-COOH-44@ UIO-66-NH are weighed2Adding into a solution of pH 6, 100mL, 50 mg. L-1Oscillating the Nd (III) solution for 3 hours at 303K until the adsorption is saturated, filtering, and drying the composite material in an oven to obtain GO-COOH-44@ UIO-66-NH with saturated adsorption2The elution was carried out with sulfuric acid, hydrochloric acid and nitric acid at different concentrations, and the results are shown in Table 2.
TABLE 2 GO-COOH-44@ UIO-66-NH2Elution rate of adsorbent under different eluents
The results in Table 2 show that 0.5 mol. L-1HNO3The desorption effect on Nd (III) is the best, and the elution rate can reach 88.54 percent.
(VI) Cyclic adsorbent utilization Properties
100mg of adsorbent was weighed into 100mL, pH 6, and concentration 50 mg. L-1The Nd (III) solution (B) is shaken at room temperature for 3 hours for adsorption saturation, filtered and then added with 0.5 mol.L-1HNO3The solution was eluted through 5 adsorption-elution cycles with the results shown in FIG. 8. After 5 adsorption-elution cycles, GO-COOH-44@ UIO-66-NH2The adsorption rate of Nd (III) can still reach more than 85 percent, which proves that the material has good cycle performance.
(VII) stability of the adsorbent
Weighing a certain mass of GO-COOH-44@ UIO-66-NH2The adsorbent was added to solutions of different acidity, left to stand and soaked for 24 hours, the material before and after soaking was dried and weighed, and the residual weight of the material was calculated to evaluate the stability of the adsorbent, the results of which are shown in fig. 9. The residual weight of the soaked material can still be kept above 85 percent, which proves that the material has good stability. The acid solution after soaking was measured by ICP to determine whether there was zr (iv) leakage in the solution. The determination result shows that no Zr (IV) ions are contained in different acid solutions, and further proves that GO-COOH-44@ UIO-66-NH2With good stability over the range of acidity studied.
Claims (10)
1. Carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2The composite material is characterized in that chloroacetic acid modified graphene oxide GO-COOH-X and a metal organic framework UIO-66-NH are mixed2Compounding, wherein X represents GO-COOH in the mass percentage of the composite material, and X is 9, 17, 23, 33, 44 or 50 percent.
2. A carboxyl group modifier as claimed in claim 1Graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH2The preparation method is characterized by comprising the following steps:
1) preparing graphene oxide: mixing and stirring concentrated sulfuric acid, concentrated phosphoric acid and graphite powder in an ice bath for 20min, slowly adding potassium permanganate, slowly heating the solution to 313-333K for reaction for 5-6h, cooling the solution to room temperature, slowly pouring the solution into ice water, stirring, dropwise adding hydrogen peroxide until the color of the solution is changed from yellow to golden yellow, and stopping dropwise adding, wherein the golden material is graphene oxide;
2) synthesizing carboxyl modified graphene oxide: centrifuging graphene oxide, washing with water to neutrality, drying, dissolving graphene oxide in water, performing ultrasonic treatment at room temperature for 1-2h, adding sodium hydroxide and chloroacetic acid, performing ultrasonic dispersion again, adjusting the pH value of the solution to neutrality, washing with water, and drying to obtain a product named as GO-COOH;
3) metal organic framework UIO-66-NH2The synthesis of (2): dissolving zirconium tetrachloride and 2-amino terephthalic acid in N, N-dimethylformamide, adding glacial acetic acid, performing ultrasonic dispersion, putting the ultrasonic solution into a reaction kettle, cooling to room temperature after reaction, putting the product into N, N-dimethylformamide, stirring for 1h, centrifuging, washing with methanol, and performing vacuum drying at 333K to obtain UIO-66-NH2；
4) Synthesizing a carboxyl modified graphene oxide @ metal organic framework composite material: reacting UIO-66-NH2Adding GO-COOH into N, N-dimethylformamide, performing ultrasonic treatment for 20min, stirring and centrifuging the solution after ultrasonic treatment at room temperature, washing the product with methanol and water respectively, drying the product at 323K, putting the dried product into a reaction kettle, adding 30-50mL of water, performing hydrothermal reaction, and finally performing centrifugal drying on the obtained gray product to obtain a product named GO-COOH-X @ UIO-66-NH2Wherein X represents GO-COOH in the mass percentage of the composite material, and X is 9, 17, 23, 33, 44 or 50 percent.
3. The carboxyl modified graphene oxide @ metal organic framework composite GO-COOH-X @ UIO-66 as claimed in claim 2-NH2The method is characterized in that in the step 1), concentrated sulfuric acid: concentrated phosphoric acid: graphite powder: potassium permanganate 180mL ═ 150-: 10-30 mL: 1.5-2.0 g: 15 g.
4. The carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH of claim 22The method is characterized in that in the step 2), the mass ratio of graphene oxide: sodium hydroxide: chloroacetic acid ═ 0.1: 0.1-2: 1-5.
5. The carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH of claim 22The method is characterized in that in the step 3), according to the solid-liquid ratio, zirconium tetrachloride: 2-amino terephthalic acid: n, N-dimethylformamide ═ 0.2 to 0.5 g: 0.1-0.3 g: 100-.
6. The carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH of claim 22Characterized in that, in the step 3), the reaction temperature is 373-393K, and the reaction time is 12-16 h.
7. The carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH of claim 22The method is characterized in that in the step 4), the temperature of the hydrothermal reaction is 343-393K, and the time is 10-15 h.
8. The carboxyl modified graphene oxide @ metal organic framework composite material GO-COOH-X @ UIO-66-NH in claim 12The application of the neodymium iron boron adsorbent in the recovery of rare earth metal neodymium is taken as an adsorbent.
9. Use according to claim 8, characterized in that the method is as follows: adjusting the pH of the solution to 1-7 in a solution containing neodymium, adding the composite material GO-COOH-X @ UIO-66-NH according to claim 12After 12h of adsorption with shaking, elution was carried out with an eluent.
10. Use according to claim 9, wherein the eluent is 0.5 mol-L-1Nitric acid of (2).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624092A (en) * | 2021-01-13 | 2021-04-09 | 北京大学 | Amidated graphene aerogel and preparation method and application thereof |
| CN112852242A (en) * | 2021-02-03 | 2021-05-28 | 沈阳帕卡濑精有限总公司 | Water-based calcium sulfonate cavity anticorrosive coating material and preparation method and application thereof |
| CN112871145A (en) * | 2021-01-13 | 2021-06-01 | 北京大学 | Graphene material and preparation method and application thereof |
| CN113030309A (en) * | 2021-03-02 | 2021-06-25 | 浙江工业大学 | Method for detecting nitroimidazole antibiotics in honey and sample treatment method thereof |
| CN113731369A (en) * | 2021-09-17 | 2021-12-03 | 南昌航空大学 | Modified metal organic framework material and preparation method and application thereof |
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| 肖欣: "金属有机骨架材料对稀土元素吸附性能的研究", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624092A (en) * | 2021-01-13 | 2021-04-09 | 北京大学 | Amidated graphene aerogel and preparation method and application thereof |
| CN112871145A (en) * | 2021-01-13 | 2021-06-01 | 北京大学 | Graphene material and preparation method and application thereof |
| CN112871145B (en) * | 2021-01-13 | 2022-05-13 | 北京大学 | Graphene material and preparation method and application thereof |
| CN112852242A (en) * | 2021-02-03 | 2021-05-28 | 沈阳帕卡濑精有限总公司 | Water-based calcium sulfonate cavity anticorrosive coating material and preparation method and application thereof |
| CN112852242B (en) * | 2021-02-03 | 2022-03-08 | 沈阳帕卡濑精有限总公司 | Water-based calcium sulfonate cavity anticorrosive coating material and preparation method and application thereof |
| CN113030309A (en) * | 2021-03-02 | 2021-06-25 | 浙江工业大学 | Method for detecting nitroimidazole antibiotics in honey and sample treatment method thereof |
| CN113731369A (en) * | 2021-09-17 | 2021-12-03 | 南昌航空大学 | Modified metal organic framework material and preparation method and application thereof |
| CN113731369B (en) * | 2021-09-17 | 2023-05-19 | 南昌航空大学 | Modified metal organic framework material and preparation method and application thereof |
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