CN113231032A - MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbent and preparation method thereof - Google Patents

MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbent and preparation method thereof Download PDF

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CN113231032A
CN113231032A CN202011224222.3A CN202011224222A CN113231032A CN 113231032 A CN113231032 A CN 113231032A CN 202011224222 A CN202011224222 A CN 202011224222A CN 113231032 A CN113231032 A CN 113231032A
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CN113231032B (en
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李积升
盛莉莉
王相明
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Qinghai Institute of Salt Lakes Research of CAS
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    • 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]
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D59/00—Separation of different isotopes of the same chemical element
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Abstract

The invention belongs to the technical field of boron isotope separation, and particularly relates to a MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbent and its preparation method. The preparation method comprises the following steps: firstly, preparing Co-doped Fe by taking ferrous precursor as raw material3O4Then preparing tetra (4-carboxyphenyl) porphyrin by using pyrrole, methyl p-formylbenzoate and KOH solution, and doping Fe with tetra (4-carboxyphenyl) porphyrin, benzoic acid, zirconium salt and Co3O4Mixed reaction to obtain Zr-MOF/Co doped Fe3O4Subsequent doping of molybdate and L-cysteine with Fe in Zr-MOF/Co3O4The material surface reacts to obtain MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbents. The adsorbent has high separation factor and adsorption capacity and can be recycled.

Description

MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbent and preparation method thereof
Technical Field
The invention belongs to the technical field of boron isotope separation, and particularly relates to a MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbent and its preparation method.
Background
Boron is a rare non-metallic element, and is mostly present in the form of compound borax in nature, and the borax is obtained by reacting with acidBoric acid. Boron-10 (10B) And boron-11 (11B) Is two stable isotopes of boron, 19.8% and 80.2% in natural boric acid, respectively. The thermal neutron capture cross section of the boron-10 is far larger than that of the boron-11, and the capture cross section of the boron-11 is more than 7.7 ten thousand times, so that the high-abundance boron-10 efficient thermal neutron absorbent with the content of 80-85% is widely utilized. In the nuclear industry, high-abundance boron-10 simple substances and compounds can be used for manufacturing control rods of nuclear reactors; the radiation-proof material has extremely excellent radiation-proof capability due to the capability of capturing thermal neutrons, and has great application in the fields of modern industry and military; medical boron-10 derived radiation therapy is minimally invasive to the human body.
However, because the chemical properties of boron-10 and boron-11 are basically not different, the proton number, the electron number and the electron arrangement outside the atomic nucleus of the two isotopes are completely consistent, and the separation difficulty is very high. Currently, methods for separating boron isotopes mainly include a boron trifluoride chemical exchange rectification method, an ion exchange chromatography method, a laser separation method, and an adsorption separation method. However, in the industrial production, other methods are not mature, and the products of high-abundance boron-10 are mainly separated by a chemical exchange rectification method. However, the method is complex to operate and high in cost, and the separation coefficient is only 1.060 by adopting various optimal schemes. The adsorption separation method is a separation method with great potential, mainly used Metal Organic Frameworks (MOFs) have higher separation coefficients in boron isotope separation, but the MOFs have poor stability, and the separation after the boron isotopes are adsorbed is extremely difficult and cannot be recycled.
Disclosure of Invention
Aiming at the technical defects of poor stability and difficult separation of a metal organic framework in the existing adsorption separation method for extracting boron isotopes, the invention provides a MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbent and its preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
1. MoS2QDs @ Zr-MOF/Co doped Fe3O4A method for producing a boron isotope adsorbent, characterized by comprising the steps ofThe following steps:
step 1: adding a ferrous precursor into deionized water, performing ultrasonic treatment at room temperature for 8-10min to obtain a ferrous solution, adding a cobalt precursor into the ferrous solution while stirring, performing continuous ultrasonic treatment for 5-7min, dropping NaOH solution into the solution while stirring after the ultrasonic treatment is finished, and then slowly adding NaNO into the solution by placing the mixed solution in a water bath at 80-85 DEG C3Continuously stirring and reacting for 1-2h to obtain black suspension; standing the suspension for 12-15h, performing magnetic separation to obtain precipitate, washing the precipitate with anhydrous ethanol and deionized water for 3 times, and drying in a vacuum oven at 40-50 deg.C for 10-12h to obtain Co-doped Fe3O4；
Step 2: adding pyrrole and methyl p-formylbenzoate into propionic acid under the condition of heating and refluxing, and reacting for 12-15h in the dark to obtain tetra (4-carboxymethyloxyphenyl) porphyrin (TPPCOOMe); adding tetra (4-carboxylmethyl phenyl) porphyrin (TPPCOOMe) into a Tetrahydrofuran (THF)/methanol mixed solution, stirring for 15-20min, dropwise adding an alkali solution into the solution after stirring, wherein the alkali solution is a KOH solution or a NaOH solution, refluxing for 12 hours, cooling to room temperature, and removing THF and methanol in the solution by rotary evaporation to obtain a solid; adding the solid into deionized water, dropwise adding hydrochloric acid into the solution until precipitate is separated out, washing the precipitate with deionized water to neutrality, and drying at 60-70 deg.C to obtain tetra (4-carboxyphenyl) porphyrin (H)2TCPP)；
And step 3: doping zirconium salt, tetra (4-carboxyphenyl) porphyrin, benzoic acid and Co with Fe3O4Adding into N, N-Dimethylformamide (DMF), performing ultrasonic treatment for 8-10min, stirring the mixed solution at 90-95 deg.C for 6-7h, centrifuging after reaction, and washing with DMF for 3 times to obtain Zr-MOF/Co doped Fe3O4；
And 4, step 4: adding molybdate which is ammonium molybdate or sodium molybdate into a proper amount of deionized water, performing ultrasonic treatment for 3-5min, and then adding a proper amount of L-cysteine and Zr-MOF/Co doped Fe into the solution3O4Continuing to perform ultrasonic treatment for 20-30min, placing the mixed solution in the inner liner of the reaction kettle after the ultrasonic treatment is finished, reacting for 20-24h at the temperature of 190 ℃, cooling to room temperature after the reaction is finished, and using absolute ethyl alcohol to obtain a solidRepeatedly ultrasonically washing with deionized water for 5-7 times, and lyophilizing to obtain MoS2QDs @ Zr-MOF/Co doped Fe3O4A boron isotope adsorbent;
the ferrous precursor is one or more of ferrous sulfate heptahydrate, ferrous chloride, ferrous citrate, ferrous acetate and ferrous nitrate;
the cobalt precursor is Co (NO)3)2·6H2O, cobalt acetate, CoCl2·6H2O or CoSO4·7H2One or more of O;
the zirconium salt is one or more of zirconium oxychloride octahydrate, zirconium chloride, zirconium sulfate, zirconium n-propoxide and zirconium tetraethoxide.
Preferably, in the step 1, the molar ratio of cobalt ions in the cobalt precursor to ferrous ions in the ferrous precursor is 1: 9-1: 11, the molar ratio of ferrous ions in the ferrous precursor to Na ions in the NaOH solution is 1: 2.1-1: 2.5, and the ferrous ions in the ferrous precursor and NaNO are3The molar ratio of (a) to (b) is 3:1 to 4: 1; the concentration of the ferrous precursor in the ferrous solution is 0.08-0.1 g/ml (the range is preferably modified because the range of the ferrous source is expanded), and the concentration of the NaOH solution is 1 mol/L.
Preferably, the mass ratio of the pyrrole to the methyl p-formylbenzoate in the step 2 is 1: 2.3-1: 2.5, and 62-71 mmol OH is added to each gram of tetra (4-carbomethoxyphenyl) porphyrin-The volume ratio of the two aqueous alkali in the THF/methanol mixed solution is 1: 1-1: 1.5.
Preferably, 0.84-0.97 g of tetra (4-carboxyphenyl) porphyrin is added into the zirconium salt in the step 3 per millimole of zirconium ions, the molar ratio of the zirconium ions to benzoic acid in the zirconium salt is 1: 2.6-1: 3.4, and each gram of Co is doped with Fe3O4Adding zirconium salt containing 2.3-2.7 mmol of zirconium ions; the concentration of the zirconium salt in DMF is 17-20 mmol/L.
Preferably, the molar mass ratio of molybdate L-cysteine in the molybdate in the step 4 is 1: 4.5-1: 4.9, and each gram of Zr-MOF/Co is doped with Fe3O4Adding molybdate containing 16 mmol-21 mmol of molybdate radical; the concentration of molybdate in deionized water is0.01～0.013g/ml。
The invention also provides the MoS2QDs @ Zr-MOF/Co doped Fe3O4The boron isotope adsorbent is prepared by the preparation method of the boron isotope adsorbent.
Has the advantages that:
(1) co can change Fe after doping3O4Shape of (2), increase of Fe3O4The defects on the surface further improve the binding capacity of Zr-MOF and the adsorption of boron isotopes.
(2) Zr-MOF in and Co doping with Fe3O4After the compounding, the stability of the reinforced metal organic framework material can be better maintained, so that the Zr-MOF has longer service life.
(3) After the composite adsorbent, particularly Zr-MOF adsorbs boron isotope, Fe is doped due to Co3O4The method has the characteristics and action trend of keeping the Zr-MOF in the original structure, and can promote the separation of the Zr-MOF after adsorbing boron isotopes, so that the Zr-MOF can be repeatedly utilized in the boron isotope extraction process.
(4)MoS2After the Zr-MOF is wrapped by the QDs, the electron transfer efficiency of the composite material can be improved, meanwhile, the sensitivity of the Zr-based metal organic framework material to boron isotopes is improved through mutual promotion, and further, the separation coefficient during boron isotope adsorption is improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Step 1: adding ferrous sulfate heptahydrate into deionized water, and performing ultrasonic treatment at room temperature for 10min to obtain FeSO4Solution, then under stirring to FeSO4Adding Co (NO) to the solution3)2·6H2O, and continuing the ultrasonication6min, adding NaOH solution into the solution under stirring after the ultrasound is finished, and then placing the mixed solution in a water bath at 80 deg.C to slowly add NaNO into the solution3Continuously stirring and reacting for 1h to obtain black suspension; standing the suspension for 12h, performing magnetic separation to obtain precipitate, washing the precipitate with anhydrous ethanol and deionized water for 3 times, respectively, and drying in a vacuum oven at 40-50 deg.C for 10-12h to obtain Co-doped Fe3O4. Wherein Co (NO)3)2·6H2The dosage ratio of O to ferrous sulfate heptahydrate is 1mol:9mol, the dosage ratio of ferrous sulfate heptahydrate to NaOH is 1mol:2.1mol, and the ferrous sulfate heptahydrate and NaNO are3The amount ratio of (A) to (B) is 4mol:1 mol.
Step 2: adding pyrrole and methyl p-formylbenzoate into propionic acid under the condition of heating reflux to react for 12h in the dark to obtain TPPCOOMe; adding TPPCOOMe into the THF/methanol mixed solution, stirring for 15-20min, dripping KOH solution into the solution after stirring is finished, refluxing for 12 hours, cooling to room temperature, and removing THF and methanol in the solution by rotary evaporation to obtain a solid; adding the solid into deionized water, dropwise adding hydrochloric acid into the solution until precipitate is separated out, washing the precipitate with deionized water to neutrality, and drying at 60-70 deg.C to obtain H2TCPP. Wherein the dosage ratio of pyrrole to methyl p-formylbenzoate is 1g:2.5g, the dosage ratio of TPPCOOMe to KOH is 1g:3.5g, and the volume ratio of the two in THF/methanol mixed solution is 1: 1.5.
And step 3: ZrOCl2·8H2O、H2TCPP, benzoic acid and Co-doped Fe3O4Adding into appropriate amount of DMF, performing ultrasonic treatment for 10min, stirring the mixed solution at 90-95 deg.C for 6-7h, centrifuging after reaction, and washing with DMF for 3 times to obtain Zr-MOF/Co doped Fe3O4. Wherein ZrOCl2·8H2O and H2The dosage ratio of TCPP is 1g:2.6-3g, ZrOCl2·8H2The dosage ratio of O to benzoic acid is 1g:12g, ZrOCl2·8H2Doping of O and Co with Fe3O4The mass ratio of (A) to (B) is 0.75g to 1 g.
And 4, step 4: adding ammonium molybdate into deionized water, performing ultrasonic treatment for 3-5min, and adding L-cysteine and Zr-MOF/Co doped Fe into the solution3O4Continuing to perform ultrasonic treatment for 20-30min, placing the mixed solution in the inner liner of the reaction kettle after the ultrasonic treatment is finished, reacting for 20-24h at the temperature of 190 ℃, cooling to room temperature after the reaction is finished, repeatedly performing ultrasonic washing for 6 times by using absolute ethyl alcohol and deionized water, and freeze-drying to obtain MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbents. Wherein the dosage ratio of ammonium molybdate to L-cysteine is 1g:3g, and the ammonium molybdate and Zr-MOF/Co are doped with Fe3O4The dosage ratio of (A) to (B) is 3.2g to 1 g.
Example 2
Step 1: adding ferrous sulfate heptahydrate into deionized water, and performing ultrasonic treatment at room temperature for 8min to obtain FeSO4Solution, then under stirring to FeSO4Adding Co (NO) to the solution3)2·6H2O, continuing to perform ultrasonic treatment for 7min, dripping NaOH solution into the solution while stirring after the ultrasonic treatment is finished, and then placing the mixed solution into a water bath at 85 ℃ to slowly add NaNO into the solution3Continuously stirring and reacting for 2h to obtain black suspension; standing the suspension for 14h, performing magnetic separation to obtain precipitate, washing the precipitate with anhydrous ethanol and deionized water for 3 times, respectively, and drying in a vacuum oven at 40-50 deg.C for 10-12h to obtain Co-doped Fe3O4. Wherein Co (NO)3)2·6H2The dosage ratio of O to ferrous sulfate heptahydrate is 1mol:10mol, the dosage ratio of ferrous sulfate heptahydrate to NaOH is 1mol:2.5mol, the ferrous sulfate heptahydrate and NaNO3The amount ratio of (A) to (B) is 3mol to 1 mol.
Step 2: adding pyrrole and methyl p-formylbenzoate into propionic acid under the condition of heating reflux to react for 14h in the dark to obtain TPPCOOMe; adding TPPCOOMe into the THF/methanol mixed solution, stirring for 15-20min, dripping KOH solution into the solution after stirring is finished, refluxing for 12 hours, cooling to room temperature, and removing THF and methanol in the solution by rotary evaporation to obtain a solid; adding the solid into deionized water, dropwise adding hydrochloric acid into the solution until precipitate is separated out, washing the precipitate with deionized water to neutrality, and drying at 60-70 deg.C to obtain H2TCPP. Wherein the dosage ratio of pyrrole to methyl p-formylbenzoate is 1g:2.3g, the dosage ratio of TPPCOOMe to KOH is 1g:4g, and the volume ratio of the two in THF/methanol mixed solution is 1:1.
And step 3: ZrOCl2·8H2O、H2TCPP, benzoic acid and Co-doped Fe3O4Adding into appropriate amount of DMF, performing ultrasonic treatment for 8min, stirring the mixed solution at 90-95 deg.C for 6-7h, centrifuging after reaction, and washing with DMF for 3 times to obtain Zr-MOF/Co doped Fe3O4. Wherein ZrOCl2·8H2O and H2The dosage ratio of TCPP is 1g:2.6-3g, ZrOCl2·8H2The dosage ratio of O to benzoic acid is 1g:11g, ZrOCl2·8H2Doping of O and Co with Fe3O4The mass ratio of (A) to (B) is 0.88g to 1 g.
And 4, step 4: adding ammonium molybdate into deionized water, performing ultrasonic treatment for 3-5min, and adding L-cysteine and Zr-MOF/Co doped Fe into the solution3O4Continuing to perform ultrasonic treatment for 20-30min, placing the mixed solution in the inner liner of the reaction kettle after the ultrasonic treatment is finished, reacting for 20-24h at the temperature of 190 ℃, cooling to room temperature after the reaction is finished, repeatedly performing ultrasonic washing for 7 times by using absolute ethyl alcohol and deionized water, and freeze-drying to obtain MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbents. Wherein the dosage ratio of ammonium molybdate to L-cysteine is 1g:2.9g, and the ammonium molybdate and Zr-MOF/Co are doped with Fe3O4The dosage ratio of (A) to (B) is 4g to 1 g.
Example 3
Step 1: adding ferrous sulfate heptahydrate into deionized water, and performing ultrasonic treatment at room temperature for 9min to obtain FeSO4Solution, then under stirring to FeSO4Adding Co (NO) to the solution3)2·6H2O, continuing to perform ultrasonic treatment for 5min, dripping NaOH solution into the solution while stirring after the ultrasonic treatment is finished, and then placing the mixed solution into a water bath at 82 ℃ to slowly add NaNO into the solution3Continuously stirring and reacting for 2h to obtain black suspension; standing the suspension for 15h, performing magnetic separation to obtain precipitate, washing the precipitate with anhydrous ethanol and deionized water for 3 times, respectively, and drying in a vacuum oven at 40-50 deg.C for 10-12h to obtain Co-doped Fe3O4. Wherein Co (NO)3)2·6H2The dosage ratio of O to ferrous sulfate heptahydrate is 1mol:11mol, the dosage ratio of ferrous sulfate heptahydrate to NaOH is 1mol:2.4mol, and the dosage ratio of heptahydrateFerrous sulfate hydrate and NaNO3The amount ratio of (A) to (B) is 3mol to 1 mol.
Step 2: adding pyrrole and methyl p-formylbenzoate into propionic acid under the condition of heating reflux to react for 15h in the dark to obtain TPPCOOMe; adding TPPCOOMe into the THF/methanol mixed solution, stirring for 15-20min, dripping KOH solution into the solution after stirring is finished, refluxing for 12 hours, cooling to room temperature, and removing THF and methanol in the solution by rotary evaporation to obtain a solid; adding the solid into deionized water, dropwise adding hydrochloric acid into the solution until precipitate is separated out, washing the precipitate with deionized water to neutrality, and drying at 60-70 deg.C to obtain H2TCPP. Wherein the dosage ratio of pyrrole to methyl p-formylbenzoate is 1g:2.4g, the dosage ratio of TPPCOOMe to KOH is 1g:3.6g, and the volume ratio of the two in THF/methanol mixed solution is 1: 1.2.
And step 3: ZrOCl2·8H2O、H2TCPP, benzoic acid and Co-doped Fe3O4Adding into appropriate amount of DMF, performing ultrasonic treatment for 9min, stirring the mixed solution at 90-95 deg.C for 6-7h, centrifuging after reaction, and washing with DMF for 3 times to obtain Zr-MOF/Co doped Fe3O4. Wherein ZrOCl2·8H2O and H2The dosage ratio of TCPP is 1g:2.6-3g, ZrOCl2·8H2The dosage ratio of O to benzoic acid is 1g:13g, ZrOCl2·8H2Doping of O and Co with Fe3O4The mass ratio of (A) to (B) is 0.79g to 1 g.
And 4, step 4: adding ammonium molybdate into deionized water, performing ultrasonic treatment for 3-5min, and adding L-cysteine and Zr-MOF/Co doped Fe into the solution3O4Continuing to perform ultrasonic treatment for 20-30min, placing the mixed solution in the inner liner of the reaction kettle after the ultrasonic treatment is finished, reacting for 20-24h at 190 ℃, cooling to room temperature after the reaction is finished, repeatedly performing ultrasonic washing for 5 times by using absolute ethyl alcohol and deionized water, and freeze-drying to obtain MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbents. Wherein the dosage ratio of ammonium molybdate to L-cysteine is 1g:2.9g, and the ammonium molybdate and Zr-MOF/Co are doped with Fe3O4The ratio of the amounts of (A) to (B) was 3.5g to 1 g.
Example 4
Step 1: ferrous sulfate heptahydrateAdding into deionized water, and performing ultrasonic treatment at room temperature for 10min to obtain FeSO4Solution, then under stirring to FeSO4Adding Co (NO) to the solution3)2·6H2O, continuing to perform ultrasonic treatment for 7min, dropping NaOH solution into the solution while stirring after the ultrasonic treatment is finished, and then placing the mixed solution into a water bath at 83 ℃ to slowly add NaNO into the solution3Continuously stirring and reacting for 1.5h to obtain black suspension; standing the suspension for 13h, performing magnetic separation to obtain precipitate, washing the precipitate with anhydrous ethanol and deionized water for 3 times, respectively, and drying in a vacuum oven at 40-50 deg.C for 10-12h to obtain Co-doped Fe3O4. Wherein Co (NO)3)2·6H2The dosage ratio of O to ferrous sulfate heptahydrate is 1mol:10.5mol, the dosage ratio of ferrous sulfate heptahydrate to NaOH is 1mol:2.3mol, and the ferrous sulfate heptahydrate and NaNO are3The amount ratio of (A) to (B) is 4mol:1 mol.
Step 2: adding pyrrole and methyl p-formylbenzoate into propionic acid under the condition of heating reflux to react for 13h in the dark to obtain TPPCOOMe; adding TPPCOOMe into the THF/methanol mixed solution, stirring for 15-20min, dripping KOH solution into the solution after stirring is finished, refluxing for 12 hours, cooling to room temperature, and removing THF and methanol in the solution by rotary evaporation to obtain a solid; adding the solid into deionized water, dropwise adding hydrochloric acid into the solution until precipitate is separated out, washing the precipitate with deionized water to neutrality, and drying at 60-70 deg.C to obtain H2TCPP. Wherein the dosage ratio of pyrrole to methyl p-formylbenzoate is 1g:2.4g, the dosage ratio of TPPCOOMe to KOH is 1g:3.8g, and the volume ratio of the two in THF/methanol mixed solution is 1: 1.4.
And step 3: ZrOCl2·8H2O、H2TCPP, benzoic acid and Co-doped Fe3O4Adding into appropriate amount of DMF, performing ultrasonic treatment for 8min, stirring the mixed solution at 90-95 deg.C for 6-7h, centrifuging after reaction, and washing with DMF for 3 times to obtain Zr-MOF/Co doped Fe3O4. Wherein ZrOCl2·8H2O and H2The dosage ratio of TCPP is 1g:2.6-3g, ZrOCl2·8H2The dosage ratio of O to benzoic acid is 1g:10g, ZrOCl2·8H2Doping of O and Co with Fe3O4The mass ratio of (A) to (B) is 0.84g to 1 g.
And 4, step 4: adding ammonium molybdate into deionized water, performing ultrasonic treatment for 3-5min, and adding L-cysteine and Zr-MOF/Co doped Fe into the solution3O4Continuing to perform ultrasonic treatment for 20-30min, placing the mixed solution in the inner liner of the reaction kettle after the ultrasonic treatment is finished, reacting for 20-24h at the temperature of 190 ℃, cooling to room temperature after the reaction is finished, repeatedly washing for 6 times by using absolute ethyl alcohol and deionized water, and freeze-drying to obtain MoS2QDs @ Zr-MOF/Co doped Fe3O4Boron isotope adsorbents. Wherein the dosage ratio of ammonium molybdate to L-cysteine is 1g:2.8g, and the ammonium molybdate and Zr-MOF/Co are doped with Fe3O4The ratio of the amounts of (A) to (B) was 3.7g to 1 g.
Comparative example 1
The preparation method according to the steps 2 to 3 of the present invention prepared the metal organic framework Zr-MOF as comparative example 1, specifically as follows
Step 1': adding pyrrole and methyl p-formylbenzoate into propionic acid under the condition of heating reflux to react for 12h in the dark to obtain TPPCOOMe; adding TPPCOOMe into the THF/methanol mixed solution, stirring for 15-20min, dripping KOH solution into the solution after stirring is finished, refluxing for 12 hours, cooling to room temperature, and removing THF and methanol in the solution by rotary evaporation to obtain a solid; adding the solid into deionized water, dropwise adding hydrochloric acid into the solution until precipitate is separated out, washing the precipitate with deionized water to neutrality, and drying at 60-70 deg.C to obtain H2TCPP. Wherein the dosage ratio of pyrrole to methyl p-formylbenzoate is 1g:2.5g, the dosage ratio of TPPCOOMe to KOH is 1g:3.5g, and the volume ratio of the two in THF/methanol mixed solution is 1: 1.5.
Step 2': ZrOCl2·8H2O、H2Adding TCPP and benzoic acid into a proper amount of DMF, performing ultrasonic treatment for 10min, then stirring the mixed solution at 90-95 ℃ for 6-7h, centrifuging after the reaction is finished, and washing for 3 times by using DMF to obtain Zr-MOF/Co doped Fe3O4. Wherein ZrOCl2·8H2O and H2The dosage ratio of TCPP is 1g:2.6-3g, ZrOCl2·8H2The dosage ratio of O to benzoic acid is 1g:12 g; obtaining Zr-MOF.
Comparative example 2
Preparing Zr-MOF/Co doped Fe according to the preparation method of the steps 1-33O4As comparative example 2, the following were specified:
step 1: adding ferrous sulfate heptahydrate into deionized water, and performing ultrasonic treatment at room temperature for 10min to obtain FeSO4Solution, then under stirring to FeSO4Adding Co (NO) to the solution3)2·6H2O, continuing to perform ultrasonic treatment for 6min, dripping NaOH solution into the solution while stirring after the ultrasonic treatment is finished, and then placing the mixed solution into a water bath at 80 ℃ to slowly add NaNO into the solution3Continuously stirring and reacting for 1h to obtain black suspension; standing the suspension for 12h, performing magnetic separation to obtain precipitate, washing the precipitate with anhydrous ethanol and deionized water for 3 times, respectively, and drying in a vacuum oven at 40-50 deg.C for 10-12h to obtain Co-doped Fe3O4. Wherein Co (NO)3)2·6H2The dosage ratio of O to ferrous sulfate heptahydrate is 1mol:9mol, the dosage ratio of ferrous sulfate heptahydrate to NaOH is 1mol:2.1mol, and the ferrous sulfate heptahydrate and NaNO are3The amount ratio of (A) to (B) is 4mol:1 mol.
Step 2: adding pyrrole and methyl p-formylbenzoate into propionic acid under the condition of heating reflux to react for 12h in the dark to obtain TPPCOOMe; adding TPPCOOMe into the THF/methanol mixed solution, stirring for 15-20min, dripping KOH solution into the solution after stirring is finished, refluxing for 12 hours, cooling to room temperature, and removing THF and methanol in the solution by rotary evaporation to obtain a solid; adding the solid into deionized water, dropwise adding hydrochloric acid into the solution until precipitate is separated out, washing the precipitate with deionized water to neutrality, and drying at 60-70 deg.C to obtain H2TCPP. Wherein the dosage ratio of pyrrole to methyl p-formylbenzoate is 1g:2.5g, the dosage ratio of TPPCOOMe to KOH is 1g:3.5g, and the volume ratio of the two in THF/methanol mixed solution is 1: 1.5.
And step 3: ZrOCl2·8H2O、H2TCPP, benzoic acid and Co-doped Fe3O4Adding into appropriate amount of DMF, performing ultrasonic treatment for 10min, stirring the mixed solution at 90-95 deg.C for 6-7h, centrifuging after reaction, and washing with DMF for 3 times to obtain Zr-MOF/Co doped Fe3O4. Wherein ZrOCl2·8H2O and H2The dosage ratio of TCPP is 1g:2.6-3g, ZrOCl2·8H2The dosage ratio of O to benzoic acid is 1g:12g, ZrOCl2·8H2Doping of O and Co with Fe3O4The mass ratio of (A) to (B) is 0.75g to 1 g. Obtaining Zr-MOF/Co doped Fe3O4。
Comparative example 3
MoS is prepared according to the preparation method of the steps 2-42QDs @ Zr-MOF was used as comparative example 3.
Step 2: adding pyrrole and methyl p-formylbenzoate into propionic acid under the condition of heating reflux to react for 12h in the dark to obtain TPPCOOMe; adding TPPCOOMe into the THF/methanol mixed solution, stirring for 15-20min, dripping KOH solution into the solution after stirring is finished, refluxing for 12 hours, cooling to room temperature, and removing THF and methanol in the solution by rotary evaporation to obtain a solid; adding the solid into deionized water, dropwise adding hydrochloric acid into the solution until precipitate is separated out, washing the precipitate with deionized water to neutrality, and drying at 60-70 deg.C to obtain H2TCPP. Wherein the dosage ratio of pyrrole to methyl p-formylbenzoate is 1g:2.5g, the dosage ratio of TPPCOOMe to KOH is 1g:3.5g, and the volume ratio of the two in THF/methanol mixed solution is 1: 1.5.
And step 3: ZrOCl2·8H2O、H2Adding TCPP and benzoic acid into a proper amount of DMF, performing ultrasonic treatment for 10min, then stirring the mixed solution at 90-95 ℃ for 6-7h, centrifuging after the reaction is finished, and washing for 3 times by using DMF to obtain Zr-MOF/Co doped Fe3O4. Wherein ZrOCl2·8H2O and H2The dosage ratio of TCPP is 1g:2.6-3g, ZrOCl2·8H2The dosage ratio of O to benzoic acid is 1g:12 g; obtaining Zr-MOF.
And 4, step 4: adding ammonium molybdate into deionized water, performing ultrasonic treatment for 3-5min, adding L-cysteine and Zr-MOF into the solution, performing ultrasonic treatment for 20-30min, placing the mixed solution into the inner liner of a reaction kettle after the ultrasonic treatment is finished, reacting for 20-24h at 190 ℃, cooling to room temperature after the reaction is finished, repeatedly performing ultrasonic washing for 6 times by using absolute ethyl alcohol and deionized water, and performing freeze-drying to obtain MoS2QDs @ Zr-MOF boron isotope adsorbents. Wherein the dosage ratio of ammonium molybdate to L-cysteine is1g:3g。
2g of the adsorbents obtained in examples 1 to 2 and comparative examples 1 to 3 were taken and added to 15ml of a boric acid solution having a concentration of 0.7mol/L, respectively, and after stirring in a water bath at 25 ℃ for 24 hours, the adsorbents were filtered, and the boron isotope separation factor and the adsorption amount of the adsorbent were obtained from the boron concentration in the residual solution.
Washing the filtered adsorbent with water for 3 times, then placing the adsorbent in ethanol for ultrasonic treatment for 8 hours, taking out the adsorbent after the ultrasonic treatment is finished, drying the adsorbent, adding the boric acid solution again according to the addition amount, and stirring the adsorbent for 24 hours at 25 ℃. The step is repeated for a plurality of times to obtain the boron isotope separation factor and the adsorption quantity after the adsorbent is repeatedly used for a plurality of times.
TABLE 1
Figure BDA0002763103760000091
Table 1 shows the boron isotope separation factors and the amounts of adsorption at the time of the first use, the second use, the fourth use and the eighth use of examples 1 to 2 and comparative examples 1 to 3 measured according to the above-mentioned methods. As can be seen from the table, the boron isotope separation factor after the first adsorption of example 1-2 was 1.5 or more, and the adsorption amount was 135mg/g or more; the separation factor of comparative examples 1 to 3 was 1.39 of comparative example 2 at the maximum, and the adsorption amount was 126mg/g of comparative example 3 at the maximum. This indicates that examples 1-2 have a boron isotope extraction ability far superior to that of comparative examples 1-3. Although the separation factor and the adsorption amount of the separation factor are reduced after the separation factor and the adsorption amount of the separation factor are reduced for a plurality of times, the reduction is not large, the separation factors of the examples 1 and 2 of the separation factors of the examples 1 and 2 of the separation factors of the examples 1 and 2 of the adsorption of the separation factors of the examples 1 and 2 of the separation factors of the examples 1.33; whereas comparative examples 1-3 show a significant decrease in performance. This demonstrates the longer useful life of examples 1-2, which can be used multiple times. Analysis of the data from comparative examples 1-3 revealed that the separation factor and adsorption capacity of comparative example 3 were greater on first use, indicating that MoS2QDs can improve the sensitivity of Zr-MOF to boron isotopes; the performance degradation of comparative example 2 was found to be less than comparative examples 1 and 3 after multiple uses, which indicates that Co is doped with Fe3O4The composition of (a) can promote the separation after boron isotope adsorption.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.

Claims (6)

1. MoS2QDs @ Zr-MOF/Co doped Fe3O4The preparation method of the boron isotope adsorbent is characterized by comprising the following steps:
step 1: adding a ferrous precursor into deionized water, performing ultrasonic treatment at room temperature for 8-10min to obtain a ferrous solution, adding a cobalt precursor into the ferrous solution while stirring, performing continuous ultrasonic treatment for 5-7min, dropping NaOH solution into the solution while stirring after the ultrasonic treatment is finished, and then slowly adding NaNO into the solution by placing the mixed solution in a water bath at 80-85 DEG C3Continuously stirring and reacting for 1-2h to obtain black suspension; standing the suspension for 12-15h, performing magnetic separation to obtain precipitate, washing the precipitate with anhydrous ethanol and deionized water for 3 times, and drying in a vacuum oven at 40-50 deg.C for 10-12h to obtain Co-doped Fe3O4；
Step 2: adding pyrrole and methyl p-formylbenzoate into propionic acid under the condition of heating and refluxing, and reacting for 12-15h in the dark to obtain tetra (4-carboxymethylphenyl) porphyrin; adding tetra (4-carboxylmethyl phenyl) porphyrin into a tetrahydrofuran/methanol mixed solution, stirring for 15-20min, dropping an alkali solution into the solution after stirring, wherein the alkali solution is a KOH solution or a NaOH solution, refluxing for 12 hours, cooling to room temperature, and removing tetrahydrofuran and methanol in the solution by rotary evaporation to obtain a solid; adding the solid into deionized water, dropwise adding hydrochloric acid into the solution until precipitate is separated out, washing the precipitate to be neutral by using the deionized water, and drying at 60-70 ℃ to obtain tetra (4-carboxyphenyl) porphyrin;
and step 3: doping zirconium salt, tetra (4-carboxyphenyl) porphyrin, benzoic acid and Co with Fe3O4Adding into N, N-dimethylformamide, performing ultrasonic treatment for 8-10min, and stirring the mixed solution at 90-95 deg.C for 6-7h, centrifuging after the reaction is finished, and washing for 3 times by using DMF (dimethyl formamide) to obtain Zr-MOF/Co doped Fe3O4；
And 4, step 4: adding molybdate which is ammonium molybdate or sodium molybdate into a proper amount of deionized water, performing ultrasonic treatment for 3-5min, and then adding a proper amount of L-cysteine and Zr-MOF/Co doped Fe into the solution3O4Continuing to perform ultrasonic treatment for 20-30min, placing the mixed solution in the inner liner of the reaction kettle after the ultrasonic treatment is finished, reacting for 20-24h at the temperature of 190 ℃, cooling to room temperature after the reaction is finished, repeatedly performing ultrasonic washing on the obtained solid for 5-7 times by using absolute ethyl alcohol and deionized water, and freeze-drying to obtain MoS2QDs @ Zr-MOF/Co doped Fe3O4A boron isotope adsorbent;
the ferrous precursor is one or more of ferrous sulfate heptahydrate, ferrous chloride, ferrous citrate, ferrous acetate and ferrous nitrate;
the cobalt precursor is Co (NO)3)2·6H2O, cobalt acetate, CoCl2·6H2O or CoSO4·7H2One or more of O;
the zirconium salt is one or more of zirconium oxychloride octahydrate, zirconium chloride, zirconium sulfate, zirconium n-propoxide and zirconium tetraethoxide.
2. A MoS according to claim 12QDs @ Zr-MOF/Co doped Fe3O4The preparation method of the boron isotope adsorbent is characterized in that in the step 1, the molar ratio of cobalt ions in the cobalt precursor to ferrous ions in the ferrous precursor is 1: 9-1: 11, the molar ratio of the ferrous ions in the ferrous precursor to Na ions in a NaOH solution is 1: 2.1-1: 2.5, and the ferrous ions in the ferrous precursor and NaNO ions are3The molar ratio of (a) to (b) is 3:1 to 4: 1; the concentration of the ferrous precursor in the ferrous solution is 0.08-0.1 g/ml, and the concentration of the NaOH solution is 1 mol/L.
3. A MoS according to claim 12QDs @ Zr-MOF/Co doped Fe3O4The preparation method of the boron isotope adsorbent is characterized in that pyrrole and p-formazan in the step 2The mass ratio of the methyl acyl benzoate to the ethyl acyl benzoate is 1: 2.3-1: 2.5, and 62-71 mmol OH is added into per gram of tetra (4-carboxymethyloxyphenyl) porphyrin-The volume ratio of the two aqueous alkali in the THF/methanol mixed solution is 1: 1-1: 1.5.
4. A MoS according to claim 12QDs @ Zr-MOF/Co doped Fe3O4The preparation method of the boron isotope adsorbent is characterized in that 0.84 g-0.97 g of tetra (4-carboxyphenyl) porphyrin is added into per millimole of zirconium ions in the zirconium salt in the step 3, the molar ratio of the zirconium ions to benzoic acid in the zirconium salt is 1: 2.6-1: 3.4, and each gram of Co is doped with Fe3O4Adding zirconium salt containing 2.3-2.7 mmol of zirconium ions; the concentration of zirconium salt in DMF is 17-20 mmol/L.
5. A MoS according to claim 12QDs @ Zr-MOF/Co doped Fe3O4The preparation method of the boron isotope adsorbent is characterized in that the molar mass ratio of molybdate L-cysteine in the molybdate in the step 4 is 1: 4.5-1: 4.9, and each gram of Zr-MOF/Co is doped with Fe3O4Adding molybdate containing 16 mmol-21 mmol of molybdate radical; the concentration of the molybdate in the deionized water is 0.01-0.13 g/ml.
6. A MoS according to any of claims 1-52QDs @ Zr-MOF/Co doped Fe3O4The boron isotope adsorbent is prepared by the preparation method of the boron isotope adsorbent.
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