CN117777478A - Iron/titanium bimetal organic framework material and normal-temperature and normal-pressure preparation method and application thereof - Google Patents
Iron/titanium bimetal organic framework material and normal-temperature and normal-pressure preparation method and application thereof Download PDFInfo
- Publication number
- CN117777478A CN117777478A CN202311742339.4A CN202311742339A CN117777478A CN 117777478 A CN117777478 A CN 117777478A CN 202311742339 A CN202311742339 A CN 202311742339A CN 117777478 A CN117777478 A CN 117777478A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- mof
- titanium
- solution
- framework material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000000463 material Substances 0.000 title claims abstract description 67
- 239000010936 titanium Substances 0.000 title claims abstract description 64
- 239000013384 organic framework Substances 0.000 title claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 16
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- -1 diammonium titanium dioxide (2-hydroxy propionic acid) Chemical compound 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 238000004108 freeze drying Methods 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- ZGRNGZSIRAIMDD-UHFFFAOYSA-L CC(C([O-])=O)O.CC(C([O-])=O)O.N.N.O.[Ti+4] Chemical compound CC(C([O-])=O)O.CC(C([O-])=O)O.N.N.O.[Ti+4] ZGRNGZSIRAIMDD-UHFFFAOYSA-L 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- QSSUXQMIQFFXCV-UHFFFAOYSA-N N.N.[Ti+4] Chemical compound N.N.[Ti+4] QSSUXQMIQFFXCV-UHFFFAOYSA-N 0.000 claims 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 13
- 231100000719 pollutant Toxicity 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 19
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 10
- 229960005309 estradiol Drugs 0.000 description 10
- 229930182833 estradiol Natural products 0.000 description 10
- 230000008901 benefit Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229960004368 oxytetracycline hydrochloride Drugs 0.000 description 5
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IFTLYVOSXXNBGD-UHFFFAOYSA-L [NH4+].[NH4+].O[Ti]O.CC(O)C([O-])=O.CC(O)C([O-])=O Chemical compound [NH4+].[NH4+].O[Ti]O.CC(O)C([O-])=O.CC(O)C([O-])=O IFTLYVOSXXNBGD-UHFFFAOYSA-L 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000000598 endocrine disruptor Substances 0.000 description 3
- 231100000049 endocrine disruptor Toxicity 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910002593 Fe-Ti Inorganic materials 0.000 description 2
- MUMGGOZAMZWBJJ-DYKIIFRCSA-N Testostosterone Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 MUMGGOZAMZWBJJ-DYKIIFRCSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 2
- 239000013082 iron-based metal-organic framework Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000013086 titanium-based metal-organic framework Substances 0.000 description 2
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- AGYAOGDEHQSPNF-UHFFFAOYSA-N [Ti].[OH-].[OH-].[NH4+].[NH4+] Chemical compound [Ti].[OH-].[OH-].[NH4+].[NH4+] AGYAOGDEHQSPNF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PCIGTTWKYUNLEP-UHFFFAOYSA-N azane;2-hydroxypropanoic acid;titanium;dihydrate Chemical compound N.N.O.O.[Ti].CC(O)C(O)=O.CC(O)C(O)=O PCIGTTWKYUNLEP-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 231100000502 fertility decrease Toxicity 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000003054 hormonal effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229960003604 testosterone Drugs 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to an iron/titanium bimetal organic framework material, and a normal-temperature and normal-pressure preparation method and application thereof, comprising the following steps of: adding ferrous sulfate heptahydrate into water, stirring and dissolving, then adding diammonium titanium dioxide (2-hydroxy propionic acid) dihydro oxide, and stirring to obtain a clear solution A; adding trimesic acid and dimethyl imidazole into an aqueous solution, and stirring to obtain a solution B; and adding the solution A into the solution B, and stirring at room temperature to finally obtain crude MOF-Fe/Ti suspension of the Fe/Ti bimetallic organic framework material. After the reaction, the suspension was centrifuged to obtain a precipitate. The precipitate was washed sequentially with pure water and ethanol and centrifuged, and finally lyophilized to obtain purified MOF-Fe/Ti. The preparation method provided by the invention is simple and easy to implement, mild in condition and high in synthesis efficiency and yield, and the prepared iron/titanium bimetal organic framework material MOF-Fe/Ti can be used for efficiently adsorbing and degrading new pollutants in water.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials and water pollution control, and particularly relates to an iron/titanium bimetal organic framework material MOF-Fe/Ti, a normal-temperature and normal-pressure preparation method and an application method thereof, and a method for adsorbing and catalyzing hydrogen peroxide to degrade new pollutants in water and an application thereof.
Background
At present, the new pollutants widely paid attention to at home and abroad mainly comprise persistent organic pollutants, endocrine disruptors, personal care products, antibiotics and the like which are regulated by international convention. The continued accumulation of endocrine disruptors in the aquatic ecosystem affects the hormonal balance of humans, leading to a number of adverse effects including reproductive disorders, reduced fertility, and induction of testosterone and breast cancers. Accumulation of antibiotics in aquatic ecology changes aquatic ecological balance, and can stimulate pathogenic bacteria to generate drug resistance and other harm. Natural decay and conventional treatment processes are ineffective in removing these new contaminants from wastewater, ground surfaces, and drinking water. In addition, the new pollutants are difficult to completely remove in the chlorination disinfection of water treatment to form disinfection byproducts such as N-nitrosodimethylamine and the like, and have potential carcinogenicity and mutagenicity.
Efficient and controllable new contaminant treatment technologies have been of great interest. The adsorption and advanced oxidation integrated technology can organically combine an adsorption method and an advanced oxidation method, and can realize effective enrichment and efficient degradation of new pollutants. This technique requires a material with a strong adsorption capacity to achieve efficient adsorption of contaminants, and generally requires a material with a high specific surface area and a high porosity to achieve this function. In addition, the adsorption material has a catalytic effect, and can be subjected to catalytic degradation on the surface of the material, so that adsorbed pollutants are efficiently degraded. The visible light Fenton technology is used as one of advanced oxidation technologies, sunlight can be effectively utilized, and the degradation efficiency of new pollutants is further improved on the basis of original Fenton catalytic degradation.
Because of the advantages of high abundance, low cost, low toxicity and the like of iron and titanium, the metal-organic frameworks of iron and titanium are widely researched and applied. When an iron-based or titanium-based metal-organic framework material is used as a catalyst, the material may provide large and dispersed active sites for contacting reactants. In addition, two different metal-built metal-organic framework materials may provide many possibilities for tuning the electronic state of the catalyst and integrating the respective properties. However, most of the iron-based metal-organic framework materials and the existing titanium-based metal-organic framework materials are synthesized under the conditions of high temperature and high pressure, long-time reaction and the like, and particularly the iron-titanium bi-metal-organic framework materials are synthesized in an organic solvent under the conditions of high temperature and high pressure. Therefore, the development of a method for safely and efficiently synthesizing the iron-titanium bimetal organic framework material at normal temperature and normal pressure with low toxicity has very important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for safely and efficiently synthesizing the Fe-Ti bimetallic organic framework material at normal temperature and pressure with low toxicity, and the Fe-Ti bimetallic organic framework material is used for adsorbing and catalyzing hydrogen peroxide to degrade new pollutants in water.
The aim of the invention can be achieved by the following technical scheme:
the first aspect of the invention provides a method for preparing an iron/titanium bimetallic organic framework material at normal temperature and normal pressure, which comprises the following steps performed at normal temperature and normal pressure:
s1: adding ferrous sulfate heptahydrate into water, stirring and dissolving, then adding diammonium titanium dioxide (2-hydroxy propionic acid) dihydro oxide, and stirring to obtain a clear solution A;
s2: adding trimesic acid and dimethyl imidazole into an aqueous solution, and stirring to obtain a solution B;
s3: adding the solution A into the solution B, and stirring to finally obtain a crude suspension of the Fe/Ti bimetallic organic framework material MOF-Fe/Ti;
s4: and centrifuging the suspension to obtain a precipitate, washing the precipitate with pure water and ethanol in sequence, centrifuging, and finally obtaining the purified iron/titanium bimetallic organic framework material MOF-Fe/Ti through freeze drying.
Further, in S1, the molar ratio of the ferrous sulfate heptahydrate to the di (2-hydroxy propionic acid) diammonium titanium dihydrogen oxide is 5:1-1:1.
Further, in S1, in the solution A, the concentration of ferrous sulfate heptahydrate is 100-800 mmol/L, and the concentration of diammonium titanium dihydroxide of di (2-hydroxy propionic acid) is 50-200 mmol/L.
Further, in S2, in the solution B, the molar concentration of the trimesic acid is 150-1000mmol/L, and the molar concentration of the dimethylimidazole is 0-500mmol/L.
Further, in S2, during MOF-Fe/Ti synthesis, dimethylimidazole is used as a base to attract protons from-COOH of trimesic acid ligands, causing negatively charged ligands to react with metal ions to form a material.
Further, the molar ratio of ferrous sulfate heptahydrate, di (2-hydroxy propionic acid) diammonium titanium hydroxide, trimesic acid and dimethyl imidazole is (1-5): 1: (2-6): (0-3).
Further, in S3, the stirring time is 2 to 48 hours.
Further, in S4, the centrifugal speed is 4000-6000 rpm, and the freeze drying condition is that the freeze drying is carried out for 24-48 hours at the temperature of minus 45 ℃ to minus 55 ℃.
The second aspect of the invention provides a MOF-Fe/Ti material prepared by the method.
The third aspect of the invention provides an application of the MOF-Fe/Ti material, wherein the MOF-Fe/Ti material is applied to light, fenton or photo-Fenton reaction conditions to adsorb and catalyze hydrogen peroxide to degrade pollutants in water.
Further, the contaminant is a new contaminant, such as estradiol or oxytetracycline hydrochloride.
The main mechanism of the invention is as follows: in the MOF-Fe/Ti synthesis process, dimethyl imidazole is used as a base, and can attract protons of-COOH from trimesic acid ligand, so that negatively charged ligand reacts with metal ions. In addition, titanium diammonium di (2-hydroxy propionate) hydroxide, as an inorganic base, can also attract part of the acid protons. Air causes slow oxidation of Fe (II) in the ferrous sulfate,can promote the combination of Fe (III) and trimesic acid anions to generate [ Fe (III) 3 (μ-O)(CO 2 ) 6 ]The secondary building block, ti (IV) may replace part of Fe (III) to form [ Fe (III) x Ti(Ⅳ) 3-x (μ-O)(CO 2 ) 6 ]And a secondary construction unit. The space-time yield of the material can be greatly improved by normal temperature and normal pressure synthesis.
Compared with the prior art, the invention has the following technical advantages:
(1) The MOF-Fe/Ti method is synthesized at normal temperature and normal pressure, and does not need to use an organic solvent as a synthesis medium.
(2) The MOF-Fe/Ti method has the advantages of low cost, simple and convenient operation, good repeatability and the like;
(3) The MOF-Fe/Ti prepared by the invention has excellent adsorption of new pollutants and catalysis of hydrogen peroxide to degrade new pollutants in water, and has wide industrial application prospect.
Drawings
FIG. 1 is a scanning electron micrograph of MOF-Fe/Ti-1 according to an embodiment of the present invention;
FIG. 2 is an XRD pattern of MOF-Fe/Ti-1 in an embodiment of the invention;
FIG. 3 is a scanning electron micrograph of MOF-Fe/Ti-2 according to an embodiment of the present invention;
FIG. 4 is an XRD pattern of MOF-Fe/Ti-2 in an embodiment of the invention;
FIG. 5 is a graph showing the effect of MOF-Fe/Ti-1 Fenton and photo Fenton on removal of estradiol in an embodiment of the invention.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. In the technical scheme, the characteristics of preparation means, materials, structures or composition ratios and the like which are not explicitly described are regarded as common technical characteristics disclosed in the prior art.
Example 1
The method for preparing the Fe/Ti bimetallic organic framework material MOF-Fe/Ti at normal temperature and normal pressure in the embodiment comprises the following steps:
(1) 556.02mg of ferrous sulfate heptahydrate is dissolved in 20mL of water, and 65 mg of ferrous sulfate heptahydrate is added3.44. Mu.L of bis (2-hydroxypropionic acid) diammonium titanium dihydroxide (50 wt.% in H) 2 O), stirring to obtain a clear solution A.
(2) 630.42mg of trimesic acid and 246.30mg of dimethyl imidazole are added to 20mL of water, and the mixture is magnetically stirred for 1h to obtain a solution B.
(3) Adding the solution A into the solution B, stirring and reacting for 24 hours at room temperature to finally obtain crude iron/titanium bimetal organic framework material MOF-Fe/Ti suspension;
(4) After completion of the reaction, the solution was centrifuged at 6000rpm for 5min to obtain a precipitate. The precipitate was washed with pure water and ethanol in this order and centrifuged at 6000rpm for 5min. After repeating the operation for 3 times, the washing was performed once more by exchanging pure water. Finally, the precipitate obtained by centrifugation is freeze-dried to obtain the purified Fe/Ti bimetallic organic framework material MOF-Fe/Ti-1.
As shown in FIG. 1, MOF-Fe/Ti-1 is mainly composed of a plurality of irregular particles with a size of 200-500 nm.
As shown in FIG. 2, the X-ray diffraction peak of MOF-Fe/Ti-1 indicates that the crystallinity of the material is good.
Example 2
The method for preparing the Fe/Ti bimetallic organic framework material MOF-Fe/Ti at normal temperature and normal pressure in the embodiment comprises the following steps:
(1) 556.02mg of ferrous sulfate heptahydrate was dissolved in 20mL of water, and 653.44. Mu.L of titanium diammonium di (2-hydroxypropionate) dihydroxide (50 wt.% in H) was added 2 O), stirring to obtain a clear solution A.
(2) 630.42mg of trimesic acid and 344.82mg of dimethyl imidazole are added to 20mL of water, and the mixture is magnetically stirred for 1h to obtain a solution B.
(3) Adding the solution A into the solution B, stirring and reacting for 24 hours at room temperature to finally obtain crude iron/titanium bimetal organic framework material MOF-Fe/Ti suspension;
(4) After completion of the reaction, the solution was centrifuged at 6000rpm for 5min to obtain a precipitate. The precipitate was washed with pure water and ethanol in this order and centrifuged at 6000rpm for 5min. After repeating the operation for 3 times, the washing was performed once more by exchanging pure water. Finally, the precipitate obtained by centrifugation is freeze-dried to obtain the purified Fe/Ti bimetallic organic framework material MOF-Fe/Ti-2.
As shown in FIG. 3, MOF-Fe/Ti-2 is in the form of long rods composed of a plurality of irregular spherical particles of 100-200 nm.
As shown in FIG. 4, the X-ray diffraction peak of MOF-Fe/Ti-2 indicates that the crystallinity of the material is good.
Example 3
The method for preparing the Fe/Ti bimetallic organic framework material MOF-Fe/Ti at normal temperature and normal pressure in the embodiment comprises the following steps:
(1) 556.02mg of ferrous sulfate heptahydrate was dissolved in 20mL of water, and 653.44. Mu.L of titanium diammonium di (2-hydroxypropionate) dihydroxide (50 wt.% in H) was added 2 O), stirring to obtain a clear solution A.
(2) The solution B was obtained by adding 630.42mg of trimesic acid to 20mL of water and magnetically stirring for 1 hour.
(3) Adding the solution A into the solution B, stirring and reacting for 24 hours at room temperature to finally obtain crude iron/titanium bimetal organic framework material MOF-Fe/Ti suspension;
(4) After completion of the reaction, the solution was centrifuged at 6000rpm for 5min to obtain a precipitate. The precipitate was washed with pure water and ethanol in this order and centrifuged at 6000rpm for 5min. After repeating the operation for 3 times, the washing was performed once more by exchanging pure water. Finally, the precipitate obtained by centrifugation is freeze-dried to obtain the purified Fe/Ti bimetallic organic framework material MOF-Fe/Ti-3.
Example 4
The method for preparing the Fe/Ti bimetallic organic framework material MOF-Fe/Ti at normal temperature and normal pressure in the embodiment comprises the following steps:
(1) 69.50g of ferrous sulfate heptahydrate was dissolved in 2L of water, and 91.68mL of titanium diammonium di (2-hydroxypropionate) dihydroxide (50 wt.% in H) was added 2 O), stirring to obtain a clear solution A.
(2) 78.75g of trimesic acid and 30.78g of dimethyl imidazole were added to 3L of water and magnetically stirred for 2 hours to obtain a solution B.
(3) Adding the solution A into the solution B, stirring and reacting for 36 hours at room temperature to finally obtain crude iron/titanium bimetal organic framework material MOF-Fe/Ti suspension;
(4) After completion of the reaction, the solution was filtered to obtain a precipitate. The precipitate was washed with pure water and ethanol in this order and filtered again. After repeating the operation for 2 times, the washing was performed once more by exchanging pure water. Finally, the precipitate obtained by filtration is subjected to freeze drying to obtain the purified Fe/Ti bimetallic organic framework material MOF-Fe/Ti-4, and the yield is about 70g.
Application example 1
The application example is the application of MOF-Fe/Ti-1 to efficiently adsorb and form antibiotic oxytetracycline hydrochloride in Fenton-like water.
For adsorption studies, 10mg of MOF-Fe/Ti-1, MOF-Fe/Ti-2, MOF-Fe/Ti-3 were added to 50mL of 100mg/L oxytetracycline hydrochloride solution, respectively. The reaction was carried out on a magnetic stirrer at 450rpm. Sample analysis was performed after 4h of adsorption. After the completion of the sampling, 0.2mL of 1M H was added 2 O 2 And (3) carrying out catalytic degradation, filtering 1.2mL of solution (a 0.22 mu m polyether sulfone filter head) into a 1.5mL centrifuge tube at the time point of 120min degradation, taking 0.5mL of filtrate into a 1.5mL sample injection vial, adding 0.5mL of methanol, mixing uniformly, and analyzing the concentration of the analyte through high performance liquid chromatography. The experimental results are shown in table 1 below:
| material name | Adsorption removal rate | Adsorption and Fenton-like removal rate |
| MOF-Fe/Ti-1 | 44.8％ | 93.6％ |
| MOF-Fe/Ti-2 | 29.8％ | 86.2％ |
| MOF-Fe/Ti-3 | 42.9％ | 95.0％ |
As can be seen from Table 1, after the MOF-Fe/Ti-1 (prepared in example 1) material was added, the adsorption efficiency for OTC reached 44.8%, and the oxidation efficiency was improved by 15% and 1.9% respectively compared with MOF-Fe/Ti-2 (prepared in example 2) and MOF-Fe/Ti-3 (prepared in example 3). MOF-Fe/Ti-1 and MOF-Fe/Ti-3 have similar Fenton-like removal effect and are 86.2 percent higher than MOF-Fe/Ti-2. Therefore, the materials have better antibiotic adsorption and Fenton-like catalytic capability.
Application example 2
The application example is the application of the MOF-Fe/Ti-1 to efficiently adsorb and degrade the estradiol which is a new pollutant in water.
Fenton-like reaction: 15mg of MOF-Fe/Ti-1 was added to 50mL of 20. Mu.M estradiol solution, respectively. The reaction was carried out on a magnetic stirrer at 450rpm. Two spots were taken at adsorption equilibrium (180 210 min). After adsorption equilibration, 100. Mu.L of 0.5M hydrogen peroxide was added to the solution, 0.8mL of the solution was taken at regular intervals and filtered into a 1.5mL sample injection vial, and the concentration of the solution was measured by high performance liquid chromatography.
Photo Fenton reaction: 15mg of MOF-Fe/Ti-1 was added to 50mL of 20. Mu.M estradiol solution, respectively. The reaction was carried out on a magnetic stirrer at 450rpm. Two spots were taken at adsorption equilibrium (180 210 min). After adsorption equilibrium, 100. Mu.L of 0.5M hydrogen peroxide is added into the solution, an LED lamp is turned on, 0.8mL of the solution is taken out at intervals and filtered into a 1.5mL sample injection vial, and the concentration of the solution is measured by high performance liquid chromatography.
As a result, as shown in FIG. 5, after adsorption equilibrium, MOF-Fe/Ti-1 can catalyze the activation of hydrogen peroxide, and 63% of estradiol can be removed within 60 minutes. MOF-Fe/Ti-1 activated hydrogen peroxide under LED illumination, and can remove more than 99% of estradiol in 90 minutes.
Comparative example 1
CN116144035a discloses an aMOF-Fe material, and a normal temperature and normal pressure preparation method and application thereof, comprising the following steps performed at normal temperature and normal pressure: adding trimesic acid into a sodium hydroxide solution, and stirring to obtain a clear solution A; ferrous sulfate heptahydrate is dissolved in water to obtain clear light green solution B; slowly adding the solution A into the solution B, and stirring to obtain a mixed liquid C; adding hydrogen peroxide solution into the mixed liquid C, and stirring at room temperature to finally obtain crude aMOF-Fe suspension; centrifuging the crude aMOF-Fe suspension, discarding the supernatant, washing the precipitate with water and ethanol in sequence, centrifuging, and freeze-drying to obtain purified aMOF-Fe.
The material prepared in the embodiment of the invention is a metal organic framework material which is double elements (Fe and Ti) and has a good crystal form, and aMOF-Fe in CN116144035A is a single element (only Fe) and is semi-amorphous. The advantages of aMOF-Fe are mainly that the synthesis of the material is quick at room temperature (usually within 4 hours), and the material has excellent adsorption performance and good catalytic effect. The advantages of MOF-Fe/Ti are mainly that the material is uniformly synthesized at room temperature in a green mode, the material adsorption performance is excellent, the optical Fenton catalysis effect is excellent, and compared with aMOF-Fe, the method can realize faster pollutant removal. The material (MOF-Fe/Ti-1) prepared by the invention has obvious photo Fenton capability advantage, hydrogen peroxide is activated under irradiation of visible light, more than 97% of oxytetracycline hydrochloride can be removed within 10min, and aMOF-Fe can only remove 73% of oxytetracycline hydrochloride. For other types of contaminants, such as the endocrine disruptor estradiol, the present material (MOF-Fe/Ti-1) activates hydrogen peroxide under visible light irradiation, over 97% of the estradiol can be removed in 60min, while the aMOF-Fe only removes 80% of the estradiol.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A method for preparing an iron/titanium bimetallic organic framework material at normal temperature and normal pressure, which is characterized by comprising the following steps of:
s1: adding ferrous sulfate heptahydrate into water, stirring and dissolving, then adding diammonium titanium dioxide (2-hydroxy propionic acid) dihydro oxide, and stirring to obtain a clear solution A;
s2: adding trimesic acid and dimethyl imidazole into an aqueous solution, and stirring to obtain a solution B;
s3: adding the solution A into the solution B, and stirring to finally obtain a crude suspension of the Fe/Ti bimetallic organic framework material MOF-Fe/Ti;
s4: and centrifuging the suspension to obtain a precipitate, washing the precipitate with pure water and ethanol in sequence, centrifuging, and finally obtaining the purified iron/titanium bimetallic organic framework material MOF-Fe/Ti through freeze drying.
2. The method for preparing the iron/titanium bimetallic organic framework material at normal temperature and normal pressure according to claim 1, wherein in S1, the adding molar ratio of the ferrous sulfate heptahydrate to the diammonium titanium dihydrogen di (2-hydroxy propionic acid) is 5:1-1:1.
3. The method for preparing the iron/titanium bimetallic organic framework material at normal temperature and normal pressure according to claim 1, wherein in S1, the concentration of ferrous sulfate heptahydrate in the solution A is 100-800 mmol/L, and the concentration of diammonium titanium dihydrogen di (2-hydroxy propionic acid) is 50-200 mmol/L.
4. The method for preparing the iron/titanium bimetallic organic framework material at normal temperature and normal pressure according to claim 1, wherein in S2, the molar concentration of trimesic acid in the solution B is 150-1000mmol/L, and the molar concentration of dimethyl imidazole is 0-500mmol/L.
5. The method for preparing an iron/titanium bimetallic organic framework material at normal temperature and pressure according to claim 1, wherein in S2, dimethyl imidazole is used as a base in the process of synthesizing MOF-Fe/Ti to attract protons of-COOH from trimesic acid ligand, so that negatively charged ligand reacts with metal ions to form the material.
6. The method for preparing the iron/titanium bimetallic organic framework material at normal temperature and normal pressure according to claim 1, wherein the addition mole ratio of ferrous sulfate heptahydrate, di (2-hydroxy propionic acid) diammonium titanium dihydrogen oxide, trimesic acid and dimethyl imidazole is (1-5): 1: (2-6): (0-3).
7. The method for preparing the iron/titanium bimetallic organic framework material at normal temperature and normal pressure according to claim 1, wherein in S3, the stirring time is 2-48 hours.
8. The method for preparing the iron/titanium bimetal organic framework material at normal temperature and normal pressure according to claim 1, wherein in S4, the centrifugal speed is 4000-6000 rpm, and the freeze drying condition is-45 ℃ to-55 ℃ and the freeze drying is 24-48 hours.
9. A MOF-Fe/Ti material prepared by the method of any one of claims 1 to 8.
10. Use of a MOF-Fe/Ti material as claimed in claim 9, wherein the MOF-Fe/Ti is used to adsorb and catalyze contaminants in hydrogen peroxide degradation water under light, fenton or photo-Fenton reaction conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311742339.4A CN117777478A (en) | 2023-12-18 | 2023-12-18 | Iron/titanium bimetal organic framework material and normal-temperature and normal-pressure preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311742339.4A CN117777478A (en) | 2023-12-18 | 2023-12-18 | Iron/titanium bimetal organic framework material and normal-temperature and normal-pressure preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117777478A true CN117777478A (en) | 2024-03-29 |
Family
ID=90387703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311742339.4A Pending CN117777478A (en) | 2023-12-18 | 2023-12-18 | Iron/titanium bimetal organic framework material and normal-temperature and normal-pressure preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117777478A (en) |
-
2023
- 2023-12-18 CN CN202311742339.4A patent/CN117777478A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jia et al. | The BiOCl/diatomite composites for rapid photocatalytic degradation of ciprofloxacin: Efficiency, toxicity evaluation, mechanisms and pathways | |
| Zhang et al. | Superoxide radical mediated persulfate activation by nitrogen doped bimetallic MOF (FeCo/N-MOF) for efficient tetracycline degradation | |
| Kong et al. | Enhanced adsorption and photocatalytic removal of PFOA from water by F-functionalized MOF with in-situ-growth TiO2: Regulation of electron density and bandgap | |
| CN110918126A (en) | Preparation method of flower-shaped molybdenum disulfide combined UiO-66 photocatalyst | |
| CN111359650B (en) | Preparation method, product and application of iron, nickel and palladium co-doped graphite-phase carbon nitride composite catalyst | |
| CN113164867B (en) | Application of fullerene and fullerene derivative composite material in degrading formaldehyde and indoor VOCs or inhibiting bacteria | |
| CN113908878B (en) | Preparation method and application of bimetallic Prussian blue analogue catalyst | |
| CN112264096B (en) | Magnetic Fenton-like catalyst based on chitosan and preparation method and application thereof | |
| CN112808233A (en) | Fe3O4Preparation method of-biochar composite nano material and method for degrading organic pollutants in water body | |
| CN110124655B (en) | Zinc oxide/carbon quantum dot composite photocatalyst and preparation method and application thereof | |
| CN114849748B (en) | CoS/Ti 3 C 2 Preparation and application of MXene composite material | |
| Mohammadiyan et al. | Synthesis and characterization of a magnetic Fe3O4@ CeO2 nanocomposite decorated with Ag nanoparticle and investigation of synergistic effects of Ag on photocatalytic activity | |
| CN111151303A (en) | Application of novel MIL-53(Fe) -based catalyst in removal of antibiotics in water | |
| Li et al. | Bimetallic Fe x Mn y catalysts derived from metal organic frameworks for efficient photocatalytic removal of quinolones without oxidant | |
| Wang et al. | Fe-complex modified cellulose acetate composite membrane with excellent photo-Fenton catalytic activity | |
| CN108927172B (en) | Preparation and application of gold nanoparticle-loaded magnetic biomass carbon material | |
| He et al. | UiO-66 with confined dyes for adsorption and visible-light photocatalytic reduction of aqueous Cr (VI) | |
| Zhang et al. | A facile fabrication of ZnFe2O4/Sepiolite composite with excellent photocatalytic performance on the removal of tetracycline hydrochloride | |
| US11896960B1 (en) | High-efficiency visible-light catalytic material and preparation method and application thereof | |
| CN113351218A (en) | Cu2O/BiFeO3Composite material and preparation method and application thereof | |
| CN117777478A (en) | Iron/titanium bimetal organic framework material and normal-temperature and normal-pressure preparation method and application thereof | |
| CN111111428A (en) | Application of fullerene and semiconductor composite material loaded by fullerene derivative in photocatalytic degradation of indoor VOCs (volatile organic compounds) | |
| CN111167464B (en) | Preparation of double Z-type V based on in-situ synthesis method2O5/FeVO4/Fe2O3Method for preparing photocatalyst and its application | |
| CN112062256A (en) | Method for treating antibiotic wastewater by using system formed by cobalt ion doped metal organic framework material and PMS | |
| CN114146689A (en) | Aluminum/cerium bimetal organic framework material, preparation method and application thereof in phosphorus adsorption and removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |