CN113651452A - Preparation method and application of porous metal organic framework material - Google Patents
Preparation method and application of porous metal organic framework material Download PDFInfo
- Publication number
- CN113651452A CN113651452A CN202110982458.1A CN202110982458A CN113651452A CN 113651452 A CN113651452 A CN 113651452A CN 202110982458 A CN202110982458 A CN 202110982458A CN 113651452 A CN113651452 A CN 113651452A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- metal salt
- framework material
- organic
- organic framework
- 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
- 239000000463 material Substances 0.000 title claims abstract description 91
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- -1 transition metal salts Chemical class 0.000 claims abstract description 75
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 72
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013110 organic ligand Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 229910001868 water Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000004729 solvothermal method Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- 239000002351 wastewater Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 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 description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 9
- 238000003760 magnetic stirring Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- UZRJWXGXZKPSJO-UHFFFAOYSA-N 9h-carbazole-3-carboxylic acid Chemical compound C1=CC=C2C3=CC(C(=O)O)=CC=C3NC2=C1 UZRJWXGXZKPSJO-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- IEKWPPTXWFKANS-UHFFFAOYSA-K trichlorocobalt Chemical compound Cl[Co](Cl)Cl IEKWPPTXWFKANS-UHFFFAOYSA-K 0.000 claims description 2
- UDBAOKKMUMKEGZ-UHFFFAOYSA-K trichloromanganese Chemical compound [Cl-].[Cl-].[Cl-].[Mn+3] UDBAOKKMUMKEGZ-UHFFFAOYSA-K 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 239000010842 industrial wastewater Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000008239 natural water Substances 0.000 abstract description 3
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 3
- 239000003651 drinking water Substances 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000001960 triggered effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 8
- 229960003405 ciprofloxacin Drugs 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000002085 persistent effect Effects 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 102000016938 Catalase Human genes 0.000 description 2
- 108010053835 Catalase Proteins 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000598 endocrine disruptor Substances 0.000 description 2
- 231100000049 endocrine disruptor Toxicity 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/48—Devices for applying magnetic or electric fields
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method and application of a porous metal organic framework material, and relates to the field of water treatment. The method comprises the following steps: dissolving at least two transition metal salts (high valence transition metal salt and low valence transition metal salt) and an organic ligand in an organic solvent, reacting by adopting a solvothermal method, cooling, carrying out solid-liquid separation, and sequentially washing and drying the obtained solid to obtain the porous metal organic framework material. Due to the synergistic effect among a plurality of metal sites, active sites are increased, the conversion of transition metal ions to a low valence state is obviously enhanced, the utilization rate of hydrogen peroxide is improved, and the catalytic activity is enhanced; the presence of low-valent transition metal in the mixed valence state makes the catalytic reaction triggered fast and has raised catalytic reaction rate. The catalyst is applied to organic wastewater treatment, has simple operation process, low material price, low treatment cost, higher catalytic performance and good stability, and can be used for advanced treatment engineering of refractory organic pollutants in drinking water, industrial wastewater and natural water.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a preparation method and application of a porous metal organic framework material.
Background
With the rapid development of urbanization and industrialization, a large amount of synthetic organic pollutants (e.g., drugs and personal care products, pesticides, dyes, etc.) are released into various types of wastewater, eventually entering natural water bodies. The vast majority of these compounds are persistent organic pollutants, have high stability and are difficult to biodegrade, and are difficult to effectively remove by traditional water treatment techniques. Many persistent organic pollutants are directly or indirectly harmful to living beings, including humans. Therefore, there is a need to develop an efficient method of removing these compounds from the environment.
The Fenton reaction (Fenton reaction) can oxidize refractory organic matters into small molecular substances, and is widely applied due to the advantages of simple operation, mild conditions, low treatment cost and the like. Metal-Organic Framework compounds (MOFs) are a novel porous material formed by self-assembling Metal ions or Metal clusters and Organic ligands, and have been used as fenton reaction catalysts for degradation treatment of Organic wastewater at present. The fenton reaction mechanism is that the oxidation-reduction cycle of ferric iron fe (iii) and ferrous iron fe (ii) activates hydrogen peroxide, thereby generating hydroxyl radicals with extremely strong oxidizing power. However, the traditional homogeneous Fenton reaction requires that the pH value is between 2 and 4, a large amount of iron mud and iron salt are generated and are difficult to recycle, and the factors limit the application of the iron mud and the iron salt in many projects. In order to overcome the defects, researchers develop a heterogeneous Fenton-like technology which has high stability, wide pH application range, no iron mud generation, easy solid-liquid separation and recycling. However, the reduction of fe (iii) to fe (ii) is the rate-limiting step of most fenton-like reactions (i.e. the transition metal species has slow valence transition), and the problems of low mass transfer efficiency and low hydrogen peroxide utilization rate still limit their further development.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of low mass transfer efficiency, low hydrogen peroxide utilization rate, slow transition metal valence state conversion and low catalytic activity when the metal organic framework compound is used as a fenton reaction catalyst to treat organic wastewater in the prior art, thereby providing a preparation method and application of a novel porous metal organic framework material.
In a first aspect, the present invention provides a method for preparing a porous metal organic framework material, comprising the following steps:
(1) dissolving at least two transition metal salts and an organic ligand in an organic solvent to obtain a mixed solution, wherein at least one transition metal salt is a high-valence transition metal salt and at least one transition metal salt is a low-valence transition metal salt;
(2) reacting the mixed solution obtained in the step (1) by adopting a solvothermal method, and cooling to room temperature to obtain a reaction suspension;
(3) carrying out solid-liquid separation on the reaction suspension obtained in the step (2);
(4) and (4) sequentially cleaning and drying the solid obtained by solid-liquid separation in the step (3) to obtain the porous metal organic framework material.
Further, in the step (1), at least one transition metal salt a and at least one transition metal salt B are added, wherein the transition metal salt a is a low valence transition metal salt, the valence of the metal ion is 1-3, and the transition metal salt B is a high valence transition metal salt, the valence of the metal ion is 1-3.
Further, the molar ratio of the metal ions in the transition metal salt A and the transition metal salt B is 1: 1 to 10.
Further, the transition metal salt a and the transition metal salt B respectively include at least one of iron salt, cobalt salt, copper salt, or manganese salt.
Further, the transition metal salt A comprises at least one of ferrous chloride, ferrous sulfate, cobalt nitrate, cobalt acetate, copper nitrate, copper chloride, copper sulfate, manganese dichloride and manganese sulfate; the transition metal salt B comprises at least one of ferric chloride, ferric sulfate, hexaammine cobalt trichloride and manganese trichloride.
Further, the organic ligand comprises at least one of terephthalic acid, fumaric acid, carbazole-3-carboxylic acid and trimesic acid; the organic solvent comprises at least one of N, N-dimethylformamide, ethanol and dimethyl sulfoxide.
Further, in the step (1), 0.41-2.08 g of transition metal salt and 0.25-0.66 g of organic ligand are added into every 30-80 mL of organic solvent, and preferably, 0.85-1.31 g of transition metal salt and 0.32-0.66 g of organic ligand are added into every 30-80 mL of organic solvent.
Further, in the step (1), after the transition metal salt and the organic ligand are added into the organic solvent, magnetic stirring is performed, wherein the rotation speed of the magnetic stirring is 500rpm, and the time is 3 hours.
Further, in the step (2), the temperature of the mixed solution for reaction is 80-160 ℃, and the time is 15-24 hours.
Further, in the step (2), the temperature of the mixed solution for reaction is 110-140 ℃ and the time is 15-20 hours.
Further, in the step (2), the mixed solution is transferred to a high-pressure reaction kettle with a 50-100 mL polytetrafluoroethylene lining, and the high-pressure reaction kettle is placed into a forced air constant-temperature drying box for reaction, wherein the volume of the mixed solution is 2/3 of the volume of the high-pressure reaction kettle.
Further, in the step (3), the solid-liquid separation adopts a high-speed centrifugal separation method, and the rotating speed is 10000-12000 r.min-1And the centrifugation time is 5-15 min.
Further, in the step (4), the washing is performed by sequentially washing with N, N-dimethylformamide, absolute ethanol and deionized water, each solvent is washed 3 times, and preferably, the washing is performed by dispersing the solid in the solvent and performing high-speed centrifugal separation.
Further, in the step (4), the drying is performed at a temperature of 40 to 60 ℃ for 12 to 15 hours.
In a second aspect, the invention provides application of the porous metal organic framework material obtained by the preparation method in organic wastewater treatment.
Further, the application comprises: and adding the porous metal organic framework material into the organic wastewater to be treated, adjusting the pH, and adding hydrogen peroxide for reaction.
Furthermore, the adding amount of the porous metal organic framework material is 0.1-0.8 g/L and the adding amount of the hydrogen peroxide is 1-10 mmol/L based on the volume of the organic wastewater.
Further, adjusting the pH value of the organic wastewater to 5-10.
Further, the reaction temperature is 20-35 ℃, and the reaction time is 5-30 min.
Further, the reaction was carried out under constant temperature in a water bath and magnetic stirring at 500 rpm.
The technical scheme of the invention has the following advantages:
1. the invention uses at least two transition metal salts (at least one low valence transition metal salt, at least one high valence transition metal salt) and organic ligand to prepare porous metal organic framework material, the organic ligand and transition metal ions with different valence states generate coordination and self-assembly reaction, the prepared material forms electron-deficient center around the group (such as benzene ring) of the organic ligand, and forms electron-rich center around a plurality of metal sites, when the material is used as Fenton reaction catalyst, electrons are continuously transferred from the electron-deficient center to the electron-rich center in the process of catalytic reaction, due to the synergistic effect among a plurality of metal sites, active sites are increased, the conversion of the transition metal ions to the low valence state is obviously enhanced, the conversion rate of the high valence transition metal to the low valence state is accelerated, the utilization rate of hydrogen peroxide is improved, and the catalytic activity is enhanced; the existence of low-valence transition metal in the mixed valence state enables the catalytic reaction to be triggered quickly, overcomes the defect of a speed limiting step, and enhances the catalytic reaction rate.
2. The preparation method of the porous metal organic framework material provided by the invention can regulate and control the reaction process, the types, the generation amount and the like of generated free radicals by adjusting the proportion of metal ions with different valence states, and has the advantage of adjustable charge distribution.
3. The preparation method of the porous metal organic framework material provided by the invention forms the porous material with large specific surface area, rich pore channel structure, high porosity and highly and uniformly dispersed active sites, is beneficial to fully exposing the reaction sites, quickens the mass transfer of reactants and promotes the contact of the reactants and the active sites.
4. The preparation method of the porous metal organic framework material provided by the invention is simple to operate and suitable for large-scale popularization and use, and the prepared material is easy to recover and has excellent water stability and chemical stability.
5. The invention also provides the application of the prepared porous metal organic framework material in organic wastewater treatment, the material has good catalytic removal effect on refractory toxic organic matters in water, the operation process is simple, the material is low in price, no extra energy is consumed, the treatment cost is low, the stability is good, the material can be applied to the deep treatment engineering of refractory organic pollutants in drinking water, industrial wastewater and natural water, and the material has good application prospect.
6. The porous metal organic framework material prepared by the invention is applied to organic wastewater treatment, has wide pH application range, does not generate iron mud, is easy for solid-liquid separation and recycling, and is environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a scanning electron microscope image 1 of a porous metal organic framework material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image 2 of the porous metal organic framework material prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of the porous metal organic framework material prepared in example 1 of the present invention;
fig. 4 is a graph showing the results of the removal rate of ciprofloxacin and total organic carbon in the recycling process of the porous metal organic framework material prepared in example 1 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
It should be noted that the higher transition metal salt and the lower transition metal salt according to the present invention depend on whether the transition metal element in the transition metal salt is in a higher valence state or a lower valence state. Specifically, when the valence of the same element in a transition metal salt is high, the transition metal salt is called a high-valence transition metal salt, and vice versa, the transition metal salt is called a low-valence transition metal salt.
For example, the iron element of ferric chloride exhibits trivalent in the compound and divalent in ferrous chloride, trivalent being a high valence state of the iron element and divalent being a low valence state of the iron element, so ferric chloride is a high valence state iron salt and ferrous chloride is a low valence state iron salt. For another example, cobalt salts in which cobalt is divalent belong to low valence cobalt salts, and trivalent cobalt salts belong to high valence cobalt salts; the copper element is monovalent copper salt belonging to low-valence copper salt, and divalent copper salt belonging to high-valence copper salt; the manganese element is bivalent manganese salt which belongs to low-valence state manganese salt, and trivalent manganese salt which belongs to high-valence state manganese salt.
The transition metal salt in a higher valence state and the transition metal salt in a lower valence state are the same element, but are not comparable if they are different elements. That is, in the at least two transition metal salts according to the present invention, the kinds of transition metals may be the same or different.
In addition, since the transition metal salt is often present in the form of a hydrate, the transition metal salt according to the present invention may be a transition metal salt present in the form of a compound or a transition metal salt present in the form of a hydrate.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The raw materials or equipment used are all conventional products which can be obtained commercially, including but not limited to the raw materials or equipment used in the examples of the present application.
Example 1
The embodiment provides a preparation method of a porous metal organic framework material, which comprises the following steps:
(1) 1.08g of FeCl3·6H2O (ferric ion concentration 50mmol/L), 0.23g Co (NO)3)2·6H2O (divalent cobalt ion concentration of 9.9mmol/L) and 0.66g of terephthalic acid (H)2BDC) is dissolved in 80mL of N, N-Dimethylformamide (DMF) to obtain a mixed solution, and the mixed solution is magnetically stirred for 3 hours at the rotating speed of 500rpm until the mixed solution is completely dissolved;
(2) transferring the mixed solution obtained in the step (1) into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the high-pressure reaction kettle into an air-blowing constant-temperature drying oven for reaction at the reaction temperature of 110 ℃ for 20 hours, and cooling the high-pressure reaction kettle to room temperature to obtain reaction suspension;
(3) carrying out high-speed centrifugal separation on the reaction suspension obtained in the step (2), wherein the rotating speed is 12000r/min, and the centrifugal time is 10 min;
(4) and (3) sequentially washing the solid obtained by high-speed centrifugal separation in the step (3) with DMF (dimethyl formamide), absolute ethyl alcohol and deionized water, washing each solvent for 3 times, and drying the solid obtained after washing in a vacuum drying oven at 60 ℃ for 12 hours to obtain the porous metal organic framework material.
Fig. 1 and 2 are scanning electron micrographs of the porous metal-organic framework material prepared in example 1 of the present invention, and fig. 3 is a transmission electron micrograph of the porous metal-organic framework material prepared in example 1 of the present invention. As can be seen from FIGS. 1 to 3, the obtained porous metal organic framework material has a three-dimensional octahedral structure, a rough surface and a diameter ranging from 500nm to 1 μm.
Example 2
The embodiment provides a preparation method of a porous metal organic framework material, which comprises the following steps:
(1) 0.65g of Cu (NO)3)2·3H2O (divalent copper ion concentration 89.7mmol/L), 0.2g MnSO4·H2O (divalent manganese ion concentration 40mmol/L) and 0.32g of trimesic acid (H)3BTC) is dissolved in 30mL of ethanol solution to obtain mixed solution, and the mixed solution is magnetically stirred for 3 hours at the rotating speed of 500rpm until the mixed solution is completely dissolved;
(2) transferring the mixed solution obtained in the step (1) into a 50mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the high-pressure reaction kettle into an air-blowing constant-temperature drying oven for reaction, wherein the reaction temperature is 140 ℃, the reaction time is 15 hours, and obtaining reaction suspension after the high-pressure reaction kettle is cooled to room temperature;
(3) carrying out high-speed centrifugal separation on the reaction suspension obtained in the step (2), wherein the rotating speed is 10000r/min, and the centrifugal time is 15 min;
(4) and (3) sequentially washing the solid obtained by high-speed centrifugal separation in the step (3) with absolute ethyl alcohol and deionized water, washing each solvent for 3 times, and drying the solid obtained after washing in a vacuum drying oven at 40 ℃ for 15 hours to obtain the porous metal organic framework material.
Comparative example 1
The comparative example provides a preparation method of a porous metal organic framework material, comprising the following steps:
(1) 1.08g of FeCl3·6H2O and 0.66g terephthalic acid (H)2BDC) is dissolved in 80mL of N, N-Dimethylformamide (DMF) to obtain a mixed solution, and the mixed solution is magnetically stirred for 3 hours at the rotating speed of 500rpm until the mixed solution is completely dissolved;
(2) transferring the mixed solution obtained in the step (1) into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the high-pressure reaction kettle into an air-blowing constant-temperature drying oven for reaction at the reaction temperature of 110 ℃ for 20 hours, and cooling the high-pressure reaction kettle to room temperature to obtain reaction suspension;
(3) carrying out high-speed centrifugal separation on the reaction suspension obtained in the step (2), wherein the rotating speed is 12000r/min, and the centrifugal time is 10 min;
(4) and (3) sequentially washing the solid obtained by high-speed centrifugal separation in the step (3) with DMF (dimethyl formamide), absolute ethyl alcohol and deionized water, washing each solvent for 3 times, and drying the solid obtained after washing in a vacuum drying oven at 60 ℃ for 12 hours to obtain the porous metal organic framework material.
Comparative example 2
The comparative example provides a preparation method of a porous metal organic framework material, comprising the following steps:
(1) 1.16g of Co (NO)3)2·6H2O and 0.66g terephthalic acid (H)2BDC) is dissolved in 80mL of N, N-Dimethylformamide (DMF) to obtain a mixed solution, and the mixed solution is magnetically stirred for 3 hours at the rotating speed of 500rpm until the mixed solution is completely dissolved;
(2) transferring the mixed solution obtained in the step (1) into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the high-pressure reaction kettle into an air-blowing constant-temperature drying oven for reaction at the reaction temperature of 110 ℃ for 20 hours, and cooling the high-pressure reaction kettle to room temperature to obtain reaction suspension;
(3) carrying out high-speed centrifugal separation on the reaction suspension obtained in the step (2), wherein the rotating speed is 12000r/min, and the centrifugal time is 10 min;
(4) and (3) sequentially washing the solid obtained by high-speed centrifugal separation in the step (3) with DMF (dimethyl formamide), absolute ethyl alcohol and deionized water, washing each solvent for 3 times, and drying the solid obtained after washing in a vacuum drying oven at 60 ℃ for 12 hours to obtain the porous metal organic framework material.
Comparative example 3
(1) 1.08g of FeCl3·6H2O (ferric ion concentration 50mmol/L), 0.14g [ Co (NH)3)6]Cl3(trivalent cobalt ion concentration 9.9mmol/L) and 0.66g of terephthalic acid (H)2BDC) is dissolved in 80mL of N, N-Dimethylformamide (DMF) to obtain a mixed solution, and the mixed solution is magnetically stirred for 3 hours at the rotating speed of 500rpm until the mixed solution is completely dissolved;
(2) transferring the mixed solution obtained in the step (1) into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the high-pressure reaction kettle into an air-blowing constant-temperature drying oven for reaction at the reaction temperature of 110 ℃ for 20 hours, and cooling the high-pressure reaction kettle to room temperature to obtain reaction suspension;
(3) carrying out high-speed centrifugal separation on the reaction suspension obtained in the step (2), wherein the rotating speed is 12000r/min, and the centrifugal time is 10 min;
(4) and (3) sequentially washing the solid obtained by high-speed centrifugal separation in the step (3) with DMF (dimethyl formamide), absolute ethyl alcohol and deionized water, washing each solvent for 3 times, and drying the solid obtained after washing in a vacuum drying oven at 60 ℃ for 12 hours to obtain the porous metal organic framework material.
Comparative example 4
The embodiment provides a preparation method of a porous metal organic framework material, which comprises the following steps:
(1) 0.65g of Cu (NO)3)2·3H2O and 0.32g trimesic acid (H)3BTC) is dissolved in 30mL of ethanol solution to obtain mixed solution, and the mixed solution is magnetically stirred for 3 hours at the rotating speed of 500rpm until the mixed solution is completely dissolved;
(2) transferring the mixed solution obtained in the step (1) into a 50mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the high-pressure reaction kettle into an air-blowing constant-temperature drying oven for reaction, wherein the reaction temperature is 140 ℃, the reaction time is 15 hours, and obtaining reaction suspension after the high-pressure reaction kettle is cooled to room temperature;
(3) carrying out high-speed centrifugal separation on the reaction suspension obtained in the step (2), wherein the rotating speed is 10000r/min, and the centrifugal time is 15 min;
(4) and (3) sequentially washing the solid obtained by high-speed centrifugal separation in the step (3) with absolute ethyl alcohol and deionized water, washing each solvent for 3 times, and drying the solid obtained after washing in a vacuum drying oven at 40 ℃ for 15 hours to obtain the porous metal organic framework material.
Comparative example 5
The embodiment provides a preparation method of a porous metal organic framework material, which comprises the following steps:
(1) 0.46g of MnSO4·H2O and 0.32g trimesic acid (H)3BTC) was dissolved in 30mL of ethanol solution,obtaining mixed liquor, and magnetically stirring the mixed liquor for 3 hours at the rotating speed of 500rpm until the mixed liquor is completely dissolved;
(2) transferring the mixed solution obtained in the step (1) into a 50mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the high-pressure reaction kettle into an air-blowing constant-temperature drying oven for reaction, wherein the reaction temperature is 140 ℃, the reaction time is 15 hours, and obtaining reaction suspension after the high-pressure reaction kettle is cooled to room temperature;
(3) carrying out high-speed centrifugal separation on the reaction suspension obtained in the step (2), wherein the rotating speed is 10000r/min, and the centrifugal time is 15 min;
(4) and (3) sequentially washing the solid obtained by high-speed centrifugal separation in the step (3) with absolute ethyl alcohol and deionized water, washing each solvent for 3 times, and drying the solid obtained after washing in a vacuum drying oven at 40 ℃ for 15 hours to obtain the porous metal organic framework material.
Comparative example 6
(1) 0.65g of Cu (NO)3)2·3H2O (divalent copper ion concentration 89.7mmol/L), 0.19g MnCl3(trivalent manganese ion concentration 40mmol/L) and 0.32g of trimesic acid (H)3BTC) is dissolved in 30mL of ethanol solution to obtain mixed solution, and the mixed solution is magnetically stirred for 3 hours at the rotating speed of 500rpm until the mixed solution is completely dissolved;
(2) transferring the mixed solution obtained in the step (1) into a 50mL high-pressure reaction kettle with a polytetrafluoroethylene lining, putting the high-pressure reaction kettle into an air-blowing constant-temperature drying oven for reaction, wherein the reaction temperature is 140 ℃, the reaction time is 15 hours, and obtaining reaction suspension after the high-pressure reaction kettle is cooled to room temperature;
(3) carrying out high-speed centrifugal separation on the reaction suspension obtained in the step (2), wherein the rotating speed is 10000r/min, and the centrifugal time is 15 min;
(4) and (3) sequentially washing the solid obtained by high-speed centrifugal separation in the step (3) with absolute ethyl alcohol and deionized water, washing each solvent for 3 times, and drying the solid obtained after washing in a vacuum drying oven at 40 ℃ for 15 hours to obtain the porous metal organic framework material.
Experimental example 1
This experimental example is used to verify the application effect of the porous metal organic framework material prepared in example 1 in the treatment of organic wastewater. The organic wastewater containing persistent organic matters is taken as a treatment object, and the total of the wastewater to be treated is four types: organic wastewater containing 20mg/L Methylene Blue (MB), organic wastewater containing 20mg/L phenol, organic wastewater containing 20mg/L bisphenol A (BPA), and organic wastewater containing 20mg/L Ciprofloxacin (CIP).
The experiment was carried out in eight groups, each group being treated as follows:
(1) experimental groups: the four organic waste waters were treated as follows:
adding the porous metal organic framework material prepared in the example 1 into organic wastewater to be treated, adjusting the pH value of the wastewater to 5, adding hydrogen peroxide at the constant temperature of 20 ℃ in a water bath and under the magnetic stirring of 500rpm, adding 5mmol/L, reacting for 30min, filtering by using a 0.22 micron filter membrane, and rapidly adding excessive catalase into the filtrate to terminate the Fenton reaction.
(2) Control group 1: the treatment method is referred to the experimental group, except that the porous metal organic framework material prepared in example 1 is replaced with the porous metal organic framework material prepared in comparative example 1;
(3) control group 2: the treatment method is referred to the experimental group, except that the porous metal organic framework material prepared in example 1 is replaced with the porous metal organic framework material prepared in comparative example 2;
(4) control group 3: the treatment method is referred to the experimental group, except that the porous metal organic framework material prepared in example 1 is replaced with the porous metal organic framework material prepared in comparative example 3;
(5) control group 4: the treatment method is referred to the experimental group, with the only difference that no hydrogen peroxide is added during the treatment;
(6) control group 5: the treatment method is referred to the experimental group, except that the porous metal organic framework material prepared in example 1 was replaced with the porous metal organic framework material prepared in comparative example 1, and hydrogen peroxide was not added during the treatment;
(7) control group 6: processing method referring to the experimental group, the only difference is that the porous metal organic framework material prepared in example 1 was replaced with the porous metal organic framework material prepared in comparative example 2, and no hydrogen peroxide was added during the processing.
(8) Control group 7: processing method referring to the experimental group, the only difference is that the porous metal organic framework material prepared in example 1 was replaced with the porous metal organic framework material prepared in comparative example 3, and hydrogen peroxide was not added during the processing.
And (3) detecting the concentrations of the residual organic matters in the wastewater treated by the experimental group and the control group 1-7 by adopting a high performance liquid chromatography, and calculating the removal rate of the persistent organic matters in various organic wastewater, wherein the results are shown in table 1.
TABLE 1 organic wastewater treatment effect of experiment group and control group 1-7
As shown in Table 1, the novel porous metal organic framework material obtained by the preparation method provided by the invention has good treatment effect on industrial wastewater containing persistent organic matters, and can efficiently degrade various organic matters such as dyes, phenols, endocrine disruptors, antibiotics and the like. Compared with a material prepared by adopting a single valence transition metal salt or a material prepared by adopting two high valence transition metal salts, the organic matter removing effect is obviously improved.
Experimental example 2
The experimental example is used for further verifying the stability of the effect of the novel porous metal organic framework material obtained by the preparation method provided by the invention on treating organic wastewater.
The organic wastewater containing 20mg/L Ciprofloxacin (CIP) was treated in the same manner as in the experimental group of example 1. And (3) circulating for 5 times, detecting the concentration of the residual ciprofloxacin and the concentration of Total Organic Carbon (TOC) in the wastewater after each treatment by respectively adopting a high performance liquid chromatograph and a TOC analyzer, and calculating the removal rate of the ciprofloxacin and the total organic carbon in the organic wastewater, wherein the result is shown in figure 4.
As can be seen from FIG. 4, the novel porous metal organic framework material obtained by the preparation method provided by the invention has good stability, and can still maintain a high removal rate after being recycled for many times.
Experimental example 3
The experimental example is used for verifying the application effect of the porous metal organic framework material prepared in the example 2 in the organic wastewater treatment. The organic wastewater containing persistent organic matters is taken as a treatment object, and the total of the wastewater to be treated is four types: organic wastewater containing 20mg/L rhodamine B (RhB), organic wastewater containing 20mg/L phenol and organic wastewater containing 20 mg/L4-chlorophenol (4-CP).
The experiment was carried out in eight groups, each group being treated as follows:
(1) experimental groups: the three organic waste waters were treated as follows:
adding the porous metal organic framework material prepared in the example 2 into organic wastewater to be treated, adjusting the pH value of the wastewater to 7, adding hydrogen peroxide at the constant temperature of 20 ℃ in a water bath and under the magnetic stirring of 500rpm, adding 6mmol/L, reacting for 30min, filtering by using a 0.22 micron filter membrane, and rapidly adding excessive catalase into the filtrate to terminate the Fenton reaction.
(2) Control group 1: the treatment method is referred to the experimental group, except that the porous metal organic framework material prepared in example 2 is replaced with the porous metal organic framework material prepared in comparative example 4;
(3) control group 2: the treatment method is referred to the experimental group, except that the porous metal organic framework material prepared in example 2 is replaced with the porous metal organic framework material prepared in comparative example 5;
(4) control group 3: the treatment method is referred to the experimental group, except that the porous metal organic framework material prepared in example 2 is replaced with the porous metal organic framework material prepared in comparative example 6;
(5) control group 4: the treatment method is referred to the experimental group, with the only difference that no hydrogen peroxide is added during the treatment;
(6) control group 5: the treatment method is referred to the experimental group, except that the porous metal organic framework material prepared in example 2 was replaced with the porous metal organic framework material prepared in comparative example 4, and hydrogen peroxide was not added during the treatment;
(7) control group 6: processing method referring to the experimental group, the only difference is that the porous metal organic framework material prepared in example 2 was replaced with the porous metal organic framework material prepared in comparative example 5, and hydrogen peroxide was not added during the processing.
(8) Control group 7: processing method referring to the experimental group, the only difference is that the porous metal organic framework material prepared in example 2 was replaced with the porous metal organic framework material prepared in comparative example 6, and hydrogen peroxide was not added during the processing.
And (3) detecting the concentrations of the residual organic matters in the wastewater treated by the experimental group and the control group 1-7 by adopting a high performance liquid chromatography, and calculating the removal rate of the persistent organic matters in various organic wastewater, wherein the results are shown in table 2.
TABLE 2 organic wastewater treatment effects of the experimental group and the control group 1-7
As shown in Table 2, the novel porous metal organic framework material obtained by the preparation method provided by the invention has good treatment effect on industrial wastewater containing persistent organic matters, and can efficiently degrade various organic matters such as dyes, phenols, endocrine disruptors and the like. Compared with a material prepared by adopting a single valence transition metal salt or a material prepared by adopting two high valence transition metal salts, the organic matter removing effect is obviously improved.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The preparation method of the porous metal organic framework material is characterized by comprising the following steps:
(1) dissolving at least two transition metal salts and an organic ligand in an organic solvent to obtain a mixed solution, wherein at least one transition metal salt is a high-valence transition metal salt and at least one transition metal salt is a low-valence transition metal salt;
(2) reacting the mixed solution obtained in the step (1) by adopting a solvothermal method, and cooling to room temperature to obtain a reaction suspension;
(3) carrying out solid-liquid separation on the reaction suspension obtained in the step (2);
(4) and (4) sequentially cleaning and drying the solid obtained by solid-liquid separation in the step (3) to obtain the porous metal organic framework material.
2. The method for preparing a porous metal organic framework material according to claim 1, wherein in step (1), at least one transition metal salt A and at least one transition metal salt B are added, wherein the transition metal salt A is a low-valence transition metal salt with a metal ion valence of 1-3, and the transition metal salt B is a high-valence transition metal salt with a metal ion valence of 1-3;
preferably, the molar ratio of the metal ions in the transition metal salt a and the transition metal salt B is 1: 1 to 10.
3. The method according to claim 2, wherein the transition metal salt A and the transition metal salt B respectively comprise at least one of iron salt, cobalt salt, copper salt or manganese salt;
preferably, the transition metal salt A comprises at least one of ferrous chloride, ferrous sulfate, cobalt nitrate, cobalt acetate, copper nitrate, copper chloride, copper sulfate, manganese dichloride and manganese sulfate; the transition metal salt B comprises at least one of ferric chloride, ferric sulfate, hexaammine cobalt trichloride and manganese trichloride.
4. The method of claim 1, wherein the organic ligand comprises at least one of terephthalic acid, fumaric acid, carbazole-3-carboxylic acid, and trimesic acid; the organic solvent comprises at least one of N, N-dimethylformamide, ethanol and dimethyl sulfoxide.
5. The method for preparing a porous metal organic framework material according to claim 1, wherein in the step (1), 0.41-2.08 g of transition metal salt and 0.25-0.66 g of organic ligand are added to 30-80 mL of organic solvent, preferably 0.85-1.31 g of transition metal salt and 0.32-0.66 g of organic ligand are added to 30-80 mL of organic solvent.
6. The method of claim 1, wherein the porous metal organic framework material is prepared by a method comprising the steps of,
in the step (1), adding an organic solvent into the transition metal salt and the organic ligand, and then carrying out magnetic stirring, wherein the rotating speed of the magnetic stirring is 500rpm, and the time is 3 hours;
in the step (2), the temperature of the mixed solution is 80-160 ℃ and the time is 15-24 hours, preferably, the temperature of the mixed solution is 110-140 ℃ and the time is 15-20 hours;
in the step (2), the mixed solution is transferred to a high-pressure reaction kettle with a polytetrafluoroethylene lining of 50-100 mL, and the high-pressure reaction kettle is placed into an air-blowing constant-temperature drying box for reaction, wherein the volume of the mixed solution accounts for 2/3 of the volume of the high-pressure reaction kettle.
7. The method of claim 1, wherein the porous metal organic framework material is prepared by a method comprising the steps of,
in the step (3), the solid-liquid separation adopts a high-speed centrifugal separation method, and the rotating speed is 10000-12000 r.min-1Centrifuging for 5-15 min;
in the step (4), the washing is sequentially carried out by using N, N-dimethylformamide, absolute ethyl alcohol and deionized water, each solvent is washed for 3 times, and preferably, the washing is carried out by dispersing solids in the solvents and carrying out high-speed centrifugal separation;
in the step (4), the drying is carried out at the temperature of 40-60 ℃ for 12-15 hours.
8. Application of the porous metal organic framework material obtained by the preparation method of any one of claims 1 to 7 in organic wastewater treatment.
9. The use according to claim 8, comprising: and adding the porous metal organic framework material into the organic wastewater to be treated, adjusting the pH, and adding hydrogen peroxide for reaction.
10. Use according to claim 9,
the adding amount of the porous metal organic framework material is 0.1-0.8 g/L and the adding amount of the hydrogen peroxide is 1-10 mmol/L based on the volume of the organic wastewater;
adjusting the pH value of the organic wastewater to 5-10;
the reaction temperature is 20-35 ℃, and the reaction time is 5-30 min;
the reaction was carried out under constant temperature in a water bath and magnetic stirring at 500 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110982458.1A CN113651452A (en) | 2021-08-25 | 2021-08-25 | Preparation method and application of porous metal organic framework material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110982458.1A CN113651452A (en) | 2021-08-25 | 2021-08-25 | Preparation method and application of porous metal organic framework material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113651452A true CN113651452A (en) | 2021-11-16 |
Family
ID=78481991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110982458.1A Pending CN113651452A (en) | 2021-08-25 | 2021-08-25 | Preparation method and application of porous metal organic framework material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113651452A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115920965A (en) * | 2022-10-14 | 2023-04-07 | 东北林业大学 | Method for preparing nanogold composite bimetallic organic framework nanoenzyme and application of peroxidase activity of nanogold composite bimetallic organic framework nanoenzyme |
| CN117487178A (en) * | 2023-10-26 | 2024-02-02 | 中南大学 | Preparation and application of metal organic framework material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753907A (en) * | 2016-02-28 | 2016-07-13 | 华南理工大学 | Synthetic method for metal organic framework containing unsaturated-coordinate mixed-valence iron center |
| CN105854944A (en) * | 2016-03-31 | 2016-08-17 | 华南理工大学 | Copper doped ferrous metal organic framework material as well as preparation method and method for activating persulfate to treat organic wastewater by using same |
| CN110841713A (en) * | 2019-10-17 | 2020-02-28 | 杭州电子科技大学 | Copper-cobalt bimetallic-organic framework material based on 2, 5-dihydroxy terephthalic acid ligand and preparation method and application thereof |
| CN112206828A (en) * | 2020-09-30 | 2021-01-12 | 浙江理工大学 | Preparation method, product and application of ferrous-doped Fe-MOFs Fenton catalyst |
-
2021
- 2021-08-25 CN CN202110982458.1A patent/CN113651452A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753907A (en) * | 2016-02-28 | 2016-07-13 | 华南理工大学 | Synthetic method for metal organic framework containing unsaturated-coordinate mixed-valence iron center |
| CN105854944A (en) * | 2016-03-31 | 2016-08-17 | 华南理工大学 | Copper doped ferrous metal organic framework material as well as preparation method and method for activating persulfate to treat organic wastewater by using same |
| CN110841713A (en) * | 2019-10-17 | 2020-02-28 | 杭州电子科技大学 | Copper-cobalt bimetallic-organic framework material based on 2, 5-dihydroxy terephthalic acid ligand and preparation method and application thereof |
| CN112206828A (en) * | 2020-09-30 | 2021-01-12 | 浙江理工大学 | Preparation method, product and application of ferrous-doped Fe-MOFs Fenton catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115920965A (en) * | 2022-10-14 | 2023-04-07 | 东北林业大学 | Method for preparing nanogold composite bimetallic organic framework nanoenzyme and application of peroxidase activity of nanogold composite bimetallic organic framework nanoenzyme |
| CN115920965B (en) * | 2022-10-14 | 2024-05-28 | 东北林业大学 | Method for preparing nano-gold composite bimetal organic framework nano-enzyme and application of peroxidase activity thereof |
| CN117487178A (en) * | 2023-10-26 | 2024-02-02 | 中南大学 | Preparation and application of metal organic framework material |
| CN117487178B (en) * | 2023-10-26 | 2024-05-28 | 中南大学 | Preparation and application of metal organic framework material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106807376B (en) | Magnetic nano composite catalyst and preparation method and application thereof | |
| CN113651452A (en) | Preparation method and application of porous metal organic framework material | |
| CN110776049B (en) | Method for treating organic wastewater by activating peroxymonosulfate with functionalized zirconium-based metal organic framework/protonated carbon nitride composite material | |
| CN108745396A (en) | A kind of nanometer of confinement Zero-valent Iron@spindle-type porous carbon catalytic oxidation method for treating water | |
| CN108246334B (en) | Functionalized ternary composite photocatalytic material and preparation method and application thereof | |
| Qiu et al. | Catalytic oxidation of the dye wastewater with hydrogen peroxide | |
| CN105478155A (en) | Regenerable heterogeneous Fenton catalyst, and preparation method and application thereof | |
| CN109482233B (en) | Ferrous metal organic framework material, normal-pressure synthesis method thereof and method for treating organic pollutants by catalytically activating persulfate | |
| CN114177927A (en) | Two-dimensional carbon nitride supported iron monatomic catalyst and preparation method and application thereof | |
| CN106475144A (en) | A kind of type Fenton catalyst preparation method based on ferrous metals organic framework material | |
| CN105233838A (en) | Preparation method of O3/H2O2 catalyst using activated bentonite as carrier, catalyst and application thereof | |
| US20210394164A1 (en) | MILLIMETER-SCALE PEROXYMONOSULFATE ACTIVATOR ZSM-5-(C@Fe) AND PREPARATION METHOD AND APPLICATION THEREOF | |
| CN114057279A (en) | Method for accelerating iron circulation by using hydrothermal carbon to promote catalytic degradation of organic pollutants | |
| CN114247444A (en) | electro-Fenton catalyst derived from iron-cobalt bimetallic organic framework and preparation method and application thereof | |
| CN111659453B (en) | Catalyst for visible light-ozone synergistic catalysis and preparation method thereof | |
| CN108083347B (en) | Preparation of cobalt ion induced flower-like cobalt manganese oxide and product and application thereof | |
| CN113941343A (en) | Sludge-based composite catalyst and preparation method and application thereof | |
| CN115318300A (en) | Preparation method of magnetic biochar with catalytic and specific phosphorus adsorption performances | |
| CN114505101A (en) | Organic dye degradation catalyst based on heterogeneous Fenton-like reaction, and preparation and application thereof | |
| CN110697862A (en) | Method for removing antibiotic resistance genes in effluent of sewage plant by using modified double metals of ginkgo leaves | |
| CN107224974B (en) | α-Fe2O3The preparation method and applications of/volcanic rock catalyst | |
| CN113600133A (en) | Phosphorus removal adsorbent and preparation method and application thereof | |
| CN113318793A (en) | Novel material for producing hydrogen peroxide and removing pollutants, and preparation method and application thereof | |
| CN108144585B (en) | Ternary magnetic composite material for heavy metal and dye wastewater treatment and preparation method thereof | |
| CN111359676A (en) | MOF-based composite material and preparation method and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211116 |
|
| RJ01 | Rejection of invention patent application after publication |