CN114405475B - Adsorption material and preparation method and application thereof - Google Patents
Adsorption material and preparation method and application thereof Download PDFInfo
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- CN114405475B CN114405475B CN202111653227.2A CN202111653227A CN114405475B CN 114405475 B CN114405475 B CN 114405475B CN 202111653227 A CN202111653227 A CN 202111653227A CN 114405475 B CN114405475 B CN 114405475B
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- 239000000463 material Substances 0.000 title claims abstract description 145
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000013082 iron-based metal-organic framework Substances 0.000 claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 239000005562 Glyphosate Substances 0.000 claims abstract description 25
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229940097068 glyphosate Drugs 0.000 claims abstract description 25
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000000575 pesticide Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000003463 adsorbent Substances 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 16
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical group OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 239000012621 metal-organic framework Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000002585 base Substances 0.000 claims 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000005389 magnetism Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 37
- 239000000243 solution Substances 0.000 description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- 239000000725 suspension Substances 0.000 description 16
- 239000011148 porous material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000011282 treatment Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 238000002336 sorption--desorption measurement Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000013291 MIL-100 Substances 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000013265 porous functional material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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
- B01J20/02—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
- B01J20/22—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
- B01J20/28—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
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an adsorption material and a preparation method and application thereof. The composition of the adsorption material of the invention comprises: an amorphous iron-based metal organic framework material and iron oxide; the iron oxide includes Fe 3 O 4 . The preparation method comprises the following steps: 1) Mixing a carbon source with alkali liquor, adding an iron source, and performing hydrothermal reaction to obtain an iron-based metal organic frame material; 2) Mixing the iron-based metal organic framework material with a solvent, slowly adding a reducing agent, and performing ultrasonic treatment to obtain the adsorption material. The adsorbing material has magnetism and abundant porous structure, has the advantages of higher adsorption capacity and convenient recycling when being used for adsorbing pesticides such as glyphosate in water, has simple preparation process, and is suitable for practical popularization and application.
Description
Technical Field
The invention belongs to the field of porous materials, and particularly relates to an adsorption material, a preparation method and application thereof.
Background
The wide use of glyphosate in agriculture as an important class of broad spectrum biocidal herbicides is of great importance for improving agricultural yield. However, the irrigation water, the rainwater and the fruit and vegetable cleaning water are very easy to introduce pesticides such as glyphosate into a circulating water system so as to influence the health of people. Therefore, research on how to effectively remove residual pesticides in water has important significance for human health.
Metal organic framework compounds (MOFs), which are a novel class of porous functional materials, have received great attention as a class of porous removal materials with great potential due to their large specific surface area, adjustable pore channel size and properties. Meanwhile, porous materials or porous composite materials with larger specific surface areas such as porous carbon materials, molecular sieves and metal organic framework compounds can be used for effectively adsorbing glyphosate pesticides, but the materials have the problems of complex preparation process, limited removal amount, difficult recycling and the like.
Therefore, there is a need to develop an adsorbent material which has a high adsorption capacity, can be recycled and is simple to prepare.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the purposes of the present invention is to provide an adsorbent.
The second object of the present invention is to provide a method for preparing an adsorbent.
It is a further object of the present invention to provide an adsorbent material for use in the same.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides an adsorbent material comprising the composition: an amorphous iron-based metal organic framework material and iron oxide; the iron oxide includes Fe 3 O 4 。
Preferably, the amorphous iron-based metal organic framework material is nano-particles, and the particle size of the nano-particles is 10-100 nm.
Further preferably, the particle diameter of the nanoparticle is 20 to 80nm.
Preferably, the adsorption material contains a porous structure formed by stacking particles of the amorphous Fe-MOF material, and the porous material has micropores and mesopores.
Further preferably, the pore diameter of the porous structure of the adsorbent is 0.1 to 20nm.
Still more preferably, the pore size of the porous structure of the adsorbent is 0.6 to 10nm.
Preferably, the adsorption capacity of the adsorption material is 280-450mg/g.
In a second aspect, the present invention provides a method for preparing the adsorption material according to the first aspect, comprising the steps of:
1) Mixing a carbon source with alkali liquor, adding an iron source, and performing hydrothermal reaction to obtain an iron-based metal organic frame material;
2) Mixing the iron-based metal organic framework material with a solvent, slowly adding a reducing agent, and performing ultrasonic treatment to obtain the adsorption material.
Preferably, step 1) further comprises stirring, wherein the stirring time is 12-48h, and the stirring temperature is 15-35 ℃.
Preferably, the alkali liquor in the step 1) is sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the solvent of the sodium hydroxide solution and/or potassium hydroxide solution is water.
Preferably, the concentration of the lye in step 1) is 0.5-2.0mol/L.
It is further preferred that the concentration of the lye in step 1) is 1.0-1.5mol/L.
Preferably, the iron salt in the step 1) is at least one of ferric nitrate, ferric chloride, ferric sulfate and ferric acetate.
Preferably, the concentration of the ferric salt in the step 1) is 0.01-0.1 mol/L.
Further preferably, the concentration of the iron salt in step 1) is 0.04 to 0.06mol/L.
Preferably, the molar ratio of the ferric salt to the trimesic acid in the step 1) is 1:1-1:6.
It is further preferred that the molar ratio of the iron salt to the trimesic acid in step 1) is 1:4.
Preferably, the temperature of the hydrothermal reaction in step 1) is 100-150 ℃.
It is further preferred that the hydrothermal reaction temperature of step 1) is 110-140 ℃.
Preferably, the hydrothermal reaction in step 1) takes 6 to 18 hours.
It is further preferred that the hydrothermal reaction in step 1) is carried out for a period of 8 to 12 hours.
Preferably, step 2) the iron-based metal organic framework material and the solvent are mixed to obtain 1-3g/L of Fe-MOF suspension.
Preferably, the reducing agent in step 2) is NaBH 4 Aqueous solution and/or KBH 4 An aqueous solution.
Preferably, the reducing agent in step 2) is added in an amount of 60-100mL.
Preferably, the NaBH 4 The concentration of the solute in the aqueous solution is 5g/L to 15g/L.
Further preferably, the NaBH 4 The concentration of the solute in the aqueous solution was 10g/L.
Preferably, in the step 2), the reducing agent is slowly added into the mixed liquid of the iron-based metal organic frame material and the solvent, and the mixed liquid of the iron-based metal organic frame material and the solvent maintains an ultrasonic state.
Preferably, the addition rate of the reducing solution in the step 2) is 0.5-20 mL/min.
It is further preferable that the addition rate of the reducing solution in the step 2) is 1 to 5mL/min.
Preferably, the time of the ultrasonic treatment in the step 2) is 20-120 min.
Further preferably, the time of the ultrasonic treatment in the step 2) is 30 to 60 minutes.
Preferably, the temperature of the ultrasound in the step 2) is 15-45 ℃.
Preferably, the power of the ultrasound in the step 2) is 50-250W.
Preferably, step 1) and step 2) further comprise washing and drying treatments.
Preferably, the number of times of washing is 2 to 6 times; the washing adopts water and ethanol.
Preferably, the drying treatment is vacuum drying; the drying temperature is 60-100 ℃; the drying time is 6-12h.
In a third aspect, the present invention provides the use of the above-described adsorbent material for the recovery of pesticides.
Preferably, the pesticide is glyphosate.
The beneficial effects of the invention are as follows:
the adsorption material is a porous amorphous metal organic framework material, has a three-dimensional structure formed by stacking magnetic, abundant micro-mesopores and smaller particle sizes, has higher adsorption capacity, and has the advantages of simple preparation method and convenient recovery and utilization.
The method comprises the following steps:
1) The adsorption material comprises an amorphous iron-based metal organic framework material and magnetic iron oxide, is environment-friendly and can be recovered simply by using a magnet.
2) The invention not only builds the magnetic porous amorphous metal organic frame material by using a simple reduction post-treatment method, treats the iron-based metal organic frame material into particles with smaller nano-size, but also can introduce mesopores to realize the effective transmission of glyphosate molecules in the pore canal so as to build the adsorbing material with higher adsorbing capacity of pesticide glyphosate and convenient recovery.
Drawings
Fig. 1 is an XRD pattern of the adsorbent material in example 1 and example 2.
Fig. 2 is an XRD pattern of the adsorbent material in comparative example 1 and comparative example 2.
Fig. 3 is an infrared spectrum of the adsorption material in example 1, example 2, comparative example 1 and comparative example 2.
Fig. 4 is a graph showing the magnetic test results of the adsorbing materials in example 1, example 2, comparative example 1 and comparative example 2.
FIG. 5 is a graph showing the comparison of the effects of the Fe-MOF suspension of example 1 before and after adsorption by a small magnet.
Fig. 6 is an SEM image of the adsorbent in example 1.
Fig. 7 is an elemental analysis chart of the adsorbent in example 1.
Fig. 8 is an SEM image of the adsorbent material in comparative example 1.
Fig. 9 is an elemental analysis chart of the adsorbent in example 1.
Fig. 10 is a nitrogen adsorption/desorption graph of the adsorption material in example 1.
FIG. 11 is a pore size distribution diagram of the adsorbent in example 1.
Fig. 12 is a nitrogen adsorption/desorption graph of the adsorption material in comparative example 1.
Fig. 13 is a pore size distribution diagram of the adsorbent in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The preparation method of the adsorption material specifically comprises the following steps:
1) 3.43g of Fe (NO) 3 ) 3 ·6H 2 Dissolving O in 145ml of water to prepare a solution A, dissolving 2.45g of trimesic acid in 68ml of 1mol/L NaOH aqueous solution to prepare a solution B, slowly adding the solution B into the solution A while stirring, continuously stirring at room temperature for 24 hours after all the solution B is added, filtering a sample, respectively washing three times by using water and absolute ethyl alcohol, and then heating in a vacuum oven at 120 ℃ for 8 hours to obtain a required iron-based metal-organic frame material (namely a yellow brown Fe-MOF material);
2) 2g of yellow brown Fe-MOF material is weighed and added into 200mL of water, ultrasonic treatment is carried out for 10min to obtain Fe-MOF suspension, and 10g/L of NaBH is slowly added into the suspension at the speed of 1mL/min 4 And (3) carrying out ultrasonic treatment (power is about 150W) on the Fe-MOF suspension liquid at room temperature (15-30 ℃) in the process of the aqueous solution (the adding amount is 60 mL), continuing ultrasonic treatment for 30min after all the Fe-MOF suspension liquid are added, washing the sample for three times by using water and absolute ethyl alcohol respectively, filtering, and then putting the sample into a vacuum oven for drying at 80 ℃ for 6h to obtain the treated adsorbing material.
Example 2
The preparation method of the adsorption material specifically comprises the following steps:
1) 3.43g of Fe (NO) 3 ) 3 ·6H 2 Dissolving O in 145ml of water to prepare a solution A, dissolving 2.45g of trimesic acid in 68ml of 1mol/L NaOH aqueous solution to prepare a solution B, slowly adding the solution B into the solution A while stirring, continuously stirring at room temperature for 24 hours after all the solution B is added, filtering a sample, respectively washing three times by using water and absolute ethyl alcohol, and then heating in a vacuum oven at 120 ℃ for 8 hours to obtain a required iron-based metal-organic frame material (namely a yellow brown Fe-MOF material);
2g of yellow brown Fe-MOF material is weighed and added into 200mL of water, ultrasonic treatment is carried out for 10min to obtain Fe-MOF suspension, and 10g/L of NaBH is slowly added into the suspension at the speed of 1mL/min 4 Aqueous solution (100 mL added) and Fe-MOF suspension in the processAnd (3) performing ultrasonic treatment (power is about 150W) at room temperature, continuing ultrasonic treatment for 30min after all the ultrasonic treatment is added, washing the sample for three times by using water and absolute ethyl alcohol respectively, filtering, and drying the sample in a vacuum oven at 80 ℃ for 6h to obtain the treated adsorbing material.
Comparative example 1
In comparison with example 1, the difference is that comparative example 1 does not include NaBH 4 The preparation process of the adsorption material of the Fe-MOF material comprises the following steps:
3.43g of Fe (NO) 3 ) 3 ·6H 2 O is dissolved in 145mL of water to prepare solution A, 2.45g of trimesic acid is dissolved in 68mL of 1mol/L NaOH aqueous solution to prepare solution B, the solution B is slowly added into the solution A at a speed of 1mL/min while stirring, stirring is continued for 24 hours at room temperature after all the solution B is added, then the sample is filtered, washed three times by water and absolute ethyl alcohol respectively, and then the solution is placed in a vacuum oven at 120 ℃ for heating treatment for 8 hours, so that an adsorption material (namely the Fe-MOF material of a yellow brown material) is obtained.
Comparative example 2
In comparison with example 1, the difference is that comparative example 2 is a rapid addition of NaBH 4 The water solution is not subjected to long-time ultrasonic treatment, and the prepared material has no magnetism and cannot be rapidly recycled, and specifically comprises the following components:
1) 3.43g of Fe (NO) 3 ) 3 ·6H 2 Dissolving O in 145ml of water to prepare a solution A, dissolving 2.45g of trimesic acid in 68ml of 1mol/L NaOH aqueous solution to prepare a solution B, slowly adding the solution B into the solution A while stirring, continuously stirring at room temperature for 24 hours after all the solution B is added, filtering a sample, respectively washing the sample with water and absolute ethyl alcohol for three times, and then heating the sample in a vacuum oven at 120 ℃ for 8 hours to obtain a required iron-based metal organic frame material (namely a yellow brown Fe-MOF material);
2) 2g of yellow brown Fe-MOF material is weighed and added into 200mL of water, the mixture is sonicated for 10min at room temperature to obtain Fe-MOF suspension, the ultrasonic power is about 150W, and 60mL of 10g/L NaBH is poured in 10 seconds 4 The aqueous solution is quickly washed by water and absolute ethyl alcohol after ultrasonic treatment for 2min, filtered and dried in a vacuum oven at 80 DEG C6h, obtaining the adsorption material.
Performance testing
The performance test method comprises the following steps:
(1) Testing of glyphosate removal
The adsorption materials obtained in the example 1, the example 2, the comparative example 1 and the comparative example 2 are added into 40mg/L glyphosate aqueous solution, the addition amount of the adsorption material is 30mg/L, and the adsorption material is fully adsorbed after shaking for 3 hours in a shaking table; then, sucking 2mL of supernatant containing the suspension of the adsorbing material and the glyphosate by using a syringe, filtering the supernatant by using a filter membrane, adding the filtered supernatant into a glass bottle, and testing the concentration of the glyphosate in the aqueous solution by using high performance liquid chromatography; the glyphosate removal of the adsorbent material was calculated and analyzed. The results of the specific glyphosate removal test are shown in Table 1.
(2) Testing of magnetic properties
The small magnet was placed next to the adsorbent powder and tested for magnetic properties and specific test results are shown in table 1 and fig. 4. The magnetic properties of the adsorbent material of example 1 in suspension were measured as shown in fig. 5.
As can be seen from fig. 4 and 5: the small magnets can pick up the adsorbing material powders of example 1 and example 2, whereas the adsorbing materials of comparative example 1 and comparative example 2 cannot be picked up. Meanwhile, the adsorption material in the embodiment 1 is prepared into 2g/L suspension, and then the small magnet is placed beside the suspension filled with the adsorption material in the embodiment 1, so that most of the adsorption material can be adsorbed by the small magnet, and therefore the suspension solution becomes clear, the stronger magnetism of the suspension solution can be illustrated, the adsorption material can be conveniently recovered in the application process, and a foundation is laid for recycling and reusing the adsorption material.
Table 1 results of performance tests of examples and comparative examples
As can be seen from table 1: the adsorption materials prepared by the invention have good glyphosate adsorption effect, the adsorption materials of the example 1 and the example 2 can have glyphosate removal amounts of 313.2mg/g and 285.5mg/g, and the glyphosate removal amounts of the adsorption materials of the comparative example 1 and the comparative example 2 are 265.4mg/g and 272.4mg/g respectively. Meanwhile, the magnetic properties of the adsorbent materials were tested with a small magnet, and it was found that the adsorbent materials of example 1 and example 2 had magnetic properties, whereas the adsorbent materials of comparative example 1 and comparative example 2 had no magnetic properties. This shows that the adsorbing material obtained by the preparation method of the invention has magnetism and higher glyphosate adsorption quantity, and is convenient for adsorbing and recovering glyphosate in solution.
Characterization of materials test
1) XRD patterns of the adsorbent materials in example 1 and example 2 are shown in fig. 1, and XRD patterns of the adsorbent materials in comparative example 1 and comparative example 2 are shown in fig. 2.
As can be seen from fig. 1: the diffraction peaks of the-MOFs in the adsorption materials of example 1 and example 2 were substantially completely disappeared, which was located at a small peak that was extremely weak at 35℃and could be considered to be Fe 3 O 4 Is a characteristic peak of (PDF # 88-0866). Fe of the adsorbing material in example 1 and example 2 3 O 4 The characteristic signal peak intensity of (c) was extremely weak, and it was revealed that the adsorption material obtained by the sodium borohydride treatment had a small amount of ferroferric oxide, and was mainly in an amorphous state, so that the adsorption materials of example 1 and example 2 had magnetism and could be attracted by the magnet.
As can be seen from fig. 2: the presence of a plurality of distinct signal peaks in the adsorption material of comparative example 1 (Fe-MOF material) indicates that the adsorption material of comparative example 1 has good crystallinity and that a portion of the characteristic peaks overlap with MIL-100 simulated peaks. Comparative example 2 is NaBH-treated 4 Solution fast-treated adsorbent material which retained the diffraction peak of part-MO material, while the characteristic peak at 44.7℃was attributed to alpha-Fe (JCPDS 06-0696), which suggests that NaBH was used 4 The adsorption material for rapid solution treatment can reduce a small amount of iron ions into elemental iron. With reference to table 1, it can be shown that the simple substance iron does not make the adsorption material magnetic, thereby facilitating recycling.
2) The infrared spectra of the adsorption materials in example 1, example 2, comparative example 1 and comparative example 2 are shown in fig. 3.
As can be seen from fig. 3: example 1, example2. The infrared spectrum peaks of the adsorption materials in comparative example 1 and comparative example 2 are substantially identical, mainly 1500cm -1 A peak of benzene ring and a peak of carboxyl on the left ligand and right ligand; and has no 2500-3200cm -1 A sawtooth peak at the location where the carboxylic acid ligand is considered protonated and cannot coordinate to the metal ion after protonation, the absence of the sawtooth peak indicates that the organic ligand can only coordinate to the ion and is not protonated. From this it can be deduced that: although the Fe-MOF material changed from crystalline to amorphous, the characteristic diffraction peak of Fe-MOF did not appear on the powder, the skeletons of the adsorbing materials in example 1 and example 2, and the coordination form of the metal ions and the ligands thereof could be maintained.
3) SEM images and elemental analysis images of the adsorption material in example 1 are shown in fig. 6 and 7. SEM images and elemental analysis images of the adsorption material in comparative example 1 are shown in fig. 8 and 9.
As can be seen from fig. 6 and 8: the adsorbent of example 1 was formed by stacking nanoparticles of 20 to 80nm. The adsorption material of comparative example 1, i.e., the Fe-MOF material not subjected to the reduction treatment with sodium borohydride solution, is apparently a stacked plate-like structure, and the size of the plate-like structure is about 200 to 500nm. This demonstrates that the slow drop and sonication of the adsorbent material with smaller nanoparticles facilitates the formation of a porous structure by stacking, and that the porous structure facilitates adsorption of glyphosate.
As can be seen from fig. 7 and 9: as a result of the elemental analysis, the adsorption material of example 1 contains Fe, C and O elements, and the mass ratio of Fe to C is about 1:1; the adsorption material of comparative example 1 also contained Fe, C and O elements, and the mass ratio of Fe to C was about 1:1.48. This indicates that during the reduction of the sodium borohydride solution, part of the ligand carboxylic acid groups break down the bond with the ions, resulting in an increase in the mass ratio of Fe to C.
The combined infrared and XRD results infer that the ligands remaining in the adsorbent material prepared in example 1 are coordinated to the metal ions, and that the detached ligands are washed away by dissolution in the organic solvent during the washing process. Due to ligand detachment and NaBH 4 Iron ions are easily reduced to a lower valence state and form oxidation with oxygenA material; with the increase of the treatment time in the aqueous solution, the low valence ions gradually become Fe 3+ The method comprises the steps of carrying out a first treatment on the surface of the So that the product has a small amount of Fe 3 O 4 . Further, in combination with SEM image, it is explained that the adsorbent material obtained in example 1 has smaller Fe 3 O 4 The nano particles are beneficial to adsorption, diffusion separation and recovery of adsorption materials.
4) The nitrogen adsorption/desorption graph and the pore size distribution diagram of the adsorption material in example 1 are shown in fig. 10 and 11, respectively. The nitrogen adsorption/desorption graph and the pore size distribution diagram of the adsorption material in comparative example 1 are shown in fig. 12 and 13, respectively.
As can be seen from fig. 10 and 11: n at 77K of the adsorbent material prepared in example 1 2 The adsorption/desorption isotherms are characteristic of a typical type IV isothermal/desorption curve, with a BET specific surface area of 182.4m 2 And/g, wherein the pore diameter is mainly distributed at 0.6-10 nm; the material of example 1 has a multi-layer micro-mesoporous structure, which provides favorable conditions for the transmission of glyphosate molecules in the pore canal, and is further favorable for improving the adsorption quantity of glyphosate.
As can be seen from fig. 12 and 13: n at 77K for the adsorbent material of comparative example 1 2 The adsorption/desorption isotherm shows the characteristic of a type I isothermal adsorption/desorption curve, and the BET specific surface area of the adsorption/desorption isotherm is 224.3m 2 The pore size distribution per gram is 0.6 to 1.5nm, and although the material of comparative example 1 has a larger BET than the material of example 1, the specific surface area of the glyphosate molecule cannot be fully utilized due to limited diffusion of the glyphosate molecule in MOF pore channels due to less mesopores, thereby being unfavorable for adsorption of the glyphosate molecule.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. An adsorbent material, wherein the composition of the adsorbent material comprises: amorphous iron-basedA metal organic framework material and an iron oxide; the iron oxide includes Fe 3 O 4 ；
The adsorption material is prepared by a preparation method comprising the following steps:
1) Mixing a carbon source with alkali liquor, adding an iron source, and performing hydrothermal reaction to obtain an iron-based metal organic frame material;
2) Mixing an iron-based metal organic framework material with a solvent, slowly adding a reducing agent, and performing ultrasonic treatment to obtain an adsorption material; wherein, in the step 2) of slowly adding the reducing agent into the mixed liquid of the iron-based metal organic frame material and the solvent, the mixed liquid of the iron-based metal organic frame material and the solvent maintains an ultrasonic state;
the addition rate of the reducing agent in the step 2) is 0.5-20 mL/min.
2. The adsorbent material of claim 1, wherein: the amorphous iron-based metal organic framework material is in a nano particle shape, and the particle size of the nano particle is 10-100 nm.
3. The adsorbent material according to claim 1 or 2, characterized in that: the adsorption material is a porous structure material with micropores and mesopores; the adsorption capacity of the adsorption material is 280-450mg/g.
4. A method of producing the adsorbent material according to any one of claims 1 to 3, comprising the steps of:
1) Mixing a carbon source with alkali liquor, adding an iron source, and performing hydrothermal reaction to obtain an iron-based metal organic frame material;
2) Mixing an iron-based metal organic framework material with a solvent, slowly adding a reducing agent, and performing ultrasonic treatment to obtain an adsorption material; wherein, in the step 2) of slowly adding the reducing agent into the mixed liquid of the iron-based metal organic frame material and the solvent, the mixed liquid of the iron-based metal organic frame material and the solvent maintains an ultrasonic state;
the addition rate of the reducing agent in the step 2) is 0.5-20 mL/min.
5. The method for producing an adsorbent material according to claim 4, wherein: the iron source in the step 1) is at least one of ferric nitrate, ferric chloride, ferric sulfate and ferric acetate; the concentration of the iron source in the step 1) is 0.01-0.1 mol/L; step 1) the molar ratio of the iron source to the carbon source is 1:1 to 1:6, preparing a base material; the carbon source is trimesic acid.
6. The method for producing an adsorbent material according to claim 4 or 5, characterized in that: the temperature of the hydrothermal reaction in the step 1) is 100-150 ℃; the time of the hydrothermal reaction in the step 1) is 6-18h.
7. The method for producing an adsorbent material according to claim 4, wherein: the reducing agent in the step 2) is NaBH 4 Aqueous solution and/or KBH 4 An aqueous solution.
8. The method for producing an adsorbent material according to claim 4 or 7, characterized in that: the concentration of the reducing agent in the step 2) is 5 g/L-15 g/L; the ultrasonic time in the step 2) is 20-120 min.
9. Use of an adsorbent material according to any one of claims 1 to 3 for the recovery of pesticides.
10. The use according to claim 9, wherein the pesticide is glyphosate.
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