CN112824588A - Method for quickly forming iron-based organic metal framework on surface of carboxylated fiber - Google Patents
Method for quickly forming iron-based organic metal framework on surface of carboxylated fiber Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 86
- 239000000835 fiber Substances 0.000 title claims abstract description 71
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 7
- 239000002184 metal Substances 0.000 title claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000011068 loading method Methods 0.000 claims abstract description 20
- 238000004043 dyeing Methods 0.000 claims abstract description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 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 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 4
- 150000002505 iron Chemical class 0.000 claims abstract description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 3
- 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 abstract 2
- 150000007524 organic acids Chemical class 0.000 claims abstract 2
- 229920000728 polyester Polymers 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 230000021523 carboxylation Effects 0.000 abstract description 5
- 238000006473 carboxylation reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000013110 organic ligand Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000013082 iron-based metal-organic framework Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- GCFAQSYBSUQUPL-UHFFFAOYSA-I pentasodium 5-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]-3-[(1,5-disulfonatonaphthalen-2-yl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].Oc1c(N=Nc2ccc3c(cccc3c2S([O-])(=O)=O)S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Nc4cccc(c4)S(=O)(=O)CCOS([O-])(=O)=O)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O GCFAQSYBSUQUPL-UHFFFAOYSA-I 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013144 Fe-MIL-100 Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a method for quickly forming an iron-based organic metal framework on the surface of a carboxylic acid fiber. The method is characterized in that firstly, the fiber is carried out carboxylation modification treatment under specific conditions, then, the fiber which is carried out carboxylation modification treatment is immersed in N, N-dimethylformamide solution containing ferric salt and carboxylic acid organic ligand mixture, and finally, MIL-Fe is rapidly generated on the surface of the carboxylated fiber and is uniformly formed by using a high-temperature high-pressure dyeing machine under the stirring condition to obtain the MIL-Fe/carboxylated fiber composite material. Wherein the iron salt can be ferric nitrate, ferric chloride or ferric sulfate, and the organic acid can be trimesic acid or terephthalic acid. The rapid forming method of the MIL-Fe loaded carboxylated fiber surface for removing pollutants by the treatment process not only can enable the MIL-Fe material to be rapidly and efficiently loaded and formed on the surface of the carboxylated fiber, but also can form the MIL-Fe film which is uniform and firm in loading, and shows excellent visible light catalytic activity and recycling performance.
Description
Technical Field
The invention relates to the technical field of organic metal framework (MOFs) new materials, in particular to a rapid and uniform forming technology of iron-based MOFs on the surface of a fiber.
Background
MOFs are organic/inorganic hybrid materials with abundant nano-pore structures formed by central metal ions or clusters and organic ligands through coordination bonds, and are combined with the functional characteristics of inorganic matters and organic matters, so that the MOFs are widely applied to environmental purification,The method has the advantages of wide application prospect in the fields of new energy, gas adsorption and separation, drug sustained release, catalysis technology and the like, and particularly in the aspect of development of new photocatalysis technology. Fe3+The ions can be used to coordinate with carboxylic acid-containing organic ligands to form iron-based metal-organic frameworks (MIL-Fe). The MIL-Fe material formed by using terephthalic acid as an organic ligand has good visible light responsiveness and excellent chemical stability, is low in preparation cost and low in environmental toxicity, and has bright application prospect in the aspect of removing organic pollutants and heavy metal ions in sewage through photocatalysis. However, the MIL-Fe material is generally in powder form and difficult to be applied industrially, so that forming the MIL-Fe material on the surface of a fiber or a membrane material to form a composite material is a key technology for application. At present, the main preparation method of the MIL-Fe material generally adopts a solvothermal or microwave-assisted method, the preparation of the MIL-Fe material takes long time and has high energy consumption, and meanwhile, the used equipment is complex and difficult to industrialize. For example, when using ferric nitrate and trimesic acid as starting materials, the reaction is not only required to be carried out in HF and HNO3In a medium, and further requires reaction at 150 ℃ under high temperature and high pressure conditions for 6 days to obtain MIL-Fe material [ Horcajada P et al, Synthesis and catalytic properties of MIL-100(Fe), an iron (III) carbonate with large pores, chem.Commun., 2007, 27: 2820-2822]. Such harsh conditions limit the mass synthesis of MIL-Fe materials and severely limit the progress of the industrialization of MIL-Fe materials. In addition, when the unsupported MIL-Fe material is directly used as a photocatalyst for degrading organic pollutants in a water body, the MIL-Fe material is difficult to completely separate from degradation liquid due to the fact that the MIL-Fe material is powdery, so that the repeated utilization rate of the MIL-Fe material is low, and secondary pollution can be brought to the natural environment. Therefore, the MIL-Fe material is loaded on the surface of the fiber or film-shaped material to form the fiber or film-shaped material, which is very favorable for separation and reuse after use. The invention provides a technical method for rapidly loading and forming an MIL-Fe material on the surface of carboxylic acid fibers by using an industrialized high-temperature high-pressure dyeing machine, which not only can rapidly and efficiently load and form the MIL-Fe material on the surface of the carboxylic acid fibers, but also can form an MIL-Fe film which is uniform and firm in loading and shows excellent visible light catalytic activity and recycling performance. The method first of allFerric salt and organic carboxylic acid ligand are dissolved in N, N-dimethylformamide, then the fiber used as a carrier is immersed in the solution, and MIL-Fe is rapidly and uniformly grown and formed on the surface of the fiber under the conditions of high temperature, high pressure and stirring, thereby effectively avoiding the use of hydrofluoric acid with high toxicity and strong corrosivity, and providing a safe and rapid MIL-Fe load forming technical method capable of being produced in large batch.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problems to be solved by the invention are as follows: provides a method for quickly forming iron-based MOFs (MIL-Fe) on the surface of carboxylic acid fiber. The method is characterized in that firstly, the fiber is carried out carboxylation modification treatment under specific conditions, and the modified fiber is immersed in N, N-dimethylformamide solution containing ferric salt and organic carboxylic acid ligand. And then, rapidly generating MIL-Fe on the surface of the carboxylated fiber by using a high-temperature high-pressure dyeing machine under the stirring condition, and uniformly forming to obtain the MIL-Fe/carboxylated fiber composite material. And finally, the photocatalyst is applied to the oxidative degradation reaction of specific organic dye as a photocatalyst to investigate the photocatalytic performance of the organic dye. It is to be noted that any oxidizing agent may not be used in the above-mentioned photocatalytic oxidative degradation reaction system. Compared with the existing hydrothermal method technology, the process disclosed by the invention has the advantages of high speed and efficiency, uniform MIL-Fe film formation, firm load, easiness in operation, moderate cost and the like. It is particularly emphasized that in the high-temperature high-pressure dyeing machine, a large number of voids are generated on the surface of the carrier fiber, so that MIL-Fe can be generated inside the surface layer of the fiber and reacts with carboxyl groups therein to enhance the bonding of MIL-Fe to the surface of the fiber. More importantly, the rapid stirring system in the high-temperature high-pressure dyeing machine ensures the uniform growth and formation of MIL-Fe on the surface of the carboxylic acid fiber.
The technical scheme for solving the problem of the load forming method is as follows: designing a load forming method of iron-based MOFs with photocatalytic characteristics on the surface of carboxylated fibers, and adopting the following process treatment:
1. preparation of a treatment solution: accurately weighing a certain amount of ferric salt and organic carboxylic acid at room temperature, respectively dissolving the ferric salt and the organic carboxylic acid in N, N-dimethylformamide, and carrying out ultrasonic treatment for 10 minutes to obtain a treatment solution, wherein the concentration of the ferric salt is 0.05-0.40 mol/L, and the concentration of the organic carboxylic acid is 0.01-0.10 mol/L.
2. And (3) a load forming process: and (3) putting 50 ml of the treatment solution into a dyeing cup of a high-temperature high-pressure dyeing machine, then putting 1 g of the carboxylic acid fiber fabric into the dyeing cup, and reacting for 4 hours at the rotation speed of 30 revolutions per minute and the temperature of 100-130 ℃ after sealing treatment so that MIL-Fe is generated on the surface of the carboxylic acid fiber fabric and is uniformly loaded and formed.
3. And (3) post-treatment: placing the obtained MIL-Fe-loaded carboxylic acid fiber in an aqueous solution containing 2.0 g/L of nonionic detergent, stirring and treating at 50 ℃ for 30 minutes to remove MIL-Fe which is not loaded firmly on the surface of the fiber, drying, and calculating the MIL-Fe loading amount (Q, mg/g) according to the following formula:
Q＝(m0/m-1)×1000
in which m and m0Respectively the mass (g) of the carboxylated fibers before and after loading MIL-Fe.
The technical method provided by the invention can be used for quickly and efficiently loading and forming the MIL-Fe material on the surface of the fiber, and the formed MIL-Fe film is uniform and firm in loading, and shows excellent visible light catalytic activity and recycling performance. Meanwhile, no high-toxicity reagent is used in the processing process, the problem of environmental pollution is avoided, the preparation cost is low, the operation is easy, and the method is favorable for producing MOFs materials on a large scale by using industrial equipment.
It is worth mentioning that the carboxylic acid fiber used in the processing process can be polycarboxylic acid modified cotton fiber, polyacrylic acid grafted polytetrafluoroethylene fiber, polyacrylic acid grafted polypropylene fiber or alkali treated polyester fiber; the iron salt may be Fe (NO)3)3、Fe2(SO4)3Or FeCl3Etc.; the organic carboxylic acid ligand may be terephthalic acid or trimesic acid, etc.
Drawings
FIG. 1 is a scanning electron microscope image of cold field emission of carboxylic acid polyester fiber (a) and MIL-Fe after loading and forming on the surface of carboxylic acid polyester fiber (b).
Fig. 2 is a photograph of MIL-Fe-loaded polyester fabrics processed according to example 3 and comparative example 3 of the present invention.
FIG. 3 shows the loading Q of MIL-Fe on the surface of the carboxylated polyester fabrics processed by the examples 1-4 and the comparative examples 1-4.
FIG. 4 is a graph showing the effect of MIL-Fe-loaded carboxylated polyester fabrics processed according to examples 1-4 and comparative examples 1-4 of the present invention on the degradation performance of dyes in water (test condition: reactive Red 195: 0.025 mmole L)-1(ii) a Catalyst: 20.0gL-1(ii) a pH 6; radiation of light: ultraviolet light (365 nm): 0.47Wcm-2Visible light (400-: 9.17mWcm-2)。
Detailed Description
The invention aims to solve the technical problem of providing a method for quickly forming MIL-Fe on the surface of carboxylic acid fiber. The method is characterized in that firstly, the fiber is carried out carboxylation modification treatment under specific conditions, and the modified fiber is immersed in N, N-dimethylformamide solution containing ferric salt and organic carboxylic acid ligand. And then, using a high-temperature high-pressure dyeing machine to rapidly generate and uniformly form MIL-Fe on the surface of the fiber under the stirring condition to obtain the MIL-Fe/polyester fiber composite material. Compared with the prior art, the process has the advantages of high speed and efficiency, uniform MIL-Fe film formation, firm load, easy operation, moderate cost and the like. It is particularly emphasized that in high temperature and high pressure dyeing machines a large number of voids are created between the fibers, allowing MIL-Fe to be generated inside the surface layer of the fibers and react with the carboxyl groups therein enhancing the bonding of MIL-Fe to the surface of the fibers. More importantly, the rapid stirring system in the high-temperature high-pressure dyeing machine ensures the uniform growth and formation of MIL-Fe on the surface of the carboxylic acid fiber. It is worth noting that the MIL-Fe prepared by the prior art uses a large amount of oxidant in the dye degradation process, which causes serious environmental pollution problem, and the invention can realize the degradation of the dye without any oxidant.
The embodiments of the present invention will be described below by taking the polyester fabric as an example, but the claims of the present invention are not limited to these embodiments.
Example 1
1. Carboxylic acid modification treatment of polyester fabric: firstly, placing the polyester fabric in a sodium hydroxide solution with the mass fraction of 2% to ensure that the volume ratio of the mass of the fiber to the solution is 1: 50, adding an accelerant with the mass fraction of 0.2%, then placing the mixed solution in a water bath with the temperature of 95 ℃ and reacting for 1 hour under the stirring condition to obtain the carboxylated polyester fabric with the decrement rate of 35%.
2. Preparation of a treatment solution: accurately weighing a certain amount of ferric chloride and terephthalic acid at room temperature, respectively dissolving in N, N-dimethylformamide, and performing ultrasonic treatment for 10 minutes to obtain a treatment solution, wherein the concentration of the ferric chloride is 0.30 mol/L, and the concentration of the terephthalic acid is 0.10 mol/L.
3. And (3) a load forming process: and (3) putting 50 ml of the treatment liquid into a dyeing cup of a high-temperature high-pressure dyeing machine, then putting 1 g of the carboxylated polyester fabric into the dyeing cup, and reacting for 4 hours under the conditions that the rotating speed is 30 revolutions per minute and the temperature is 100 ℃ after sealing treatment so that MIL-Fe is generated on the surface of the carboxylated polyester fabric and is uniformly loaded and formed.
4. And (3) post-treatment: and (3) placing the obtained MIL-Fe-loaded carboxylated polyester fabric into an aqueous solution containing 2.0 g/L of nonionic detergent, and stirring and treating at 50 ℃ for 30 minutes to remove the non-loaded MIL-Fe on the surface of the fabric to obtain the MIL-Fe-loaded carboxylated polyester fabric with the load of 198.3 mg/g.
Example 2
1. The process was the same as the 1-step process in example 1.
2. The process was the same as the 2-step process in example 1.
3. The temperature was set at 110 ℃ and the remaining steps were the same as in example 1, 3 steps.
4. The process was the same as the 4-step process in example 1, resulting in a MIL-Fe-loaded carboxylated polyester fabric having a loading of 245.7 mg/g.
Example 3
1. The process was the same as the 1-step process in example 1.
2. The process was the same as the 2-step process in example 1.
3. The temperature was set to 120 ℃ and the remaining steps were the same as in example 1, 3 steps.
4. The process was the same as the 4-step process in example 1, resulting in a MIL-Fe-loaded carboxylated polyester fabric having a loading of 326.2 mg/g.
Example 4
1. The process was the same as the 1-step process in example 1.
2. The process was the same as the 2-step process in example 1.
3. The temperature was set at 130 ℃ and the rest of the procedure was the same as in example 1, 3 steps.
4. The process was the same as the 4-step process in example 1, resulting in a MIL-Fe-loaded carboxylated polyester fabric having a loading of 404.7 mg/g.
Comparative example
This example is a comparative example of effect. The MIL-Fe loaded carboxylated polyester fabric is prepared by a solvothermal method, and the process method comprises the following steps:
comparative example 1
1. The process was the same as the 1-step process in example 1.
2. The process was the same as the 2-step process in example 1.
3. And (3) a load forming process: and (3) putting 50 ml of the treatment solution into a reaction kettle with a polytetrafluoroethylene lining, then putting 1 g of carboxylated polyester fabric into the reaction kettle, sealing the reaction kettle, and reacting the carboxylic polyester fabric for 4 hours at 100 ℃ to generate and load MIL-Fe on the surface of the carboxylated polyester fabric.
4. The process was the same as the 4-step process in example 1, resulting in a MIL-Fe-loaded carboxylated polyester fabric having a loading of 1.05 mg/g.
Comparative example 2
1. The process was the same as the 1-step process in comparative example 1.
2. The process was the same as the 2-step process in comparative example 1.
3. The temperature was set to 110 ℃ and the remaining process was the same as the 3-step process in comparative example 1.
4. The process was the same as the 4-step process in comparative example 1, resulting in a MIL-Fe-loaded carboxylated polyester fabric having a loading of 63.2 mg/g.
Comparative example 3
1. The process was the same as the 1-step process in comparative example 1.
2. The process was the same as the 2-step process in comparative example 1.
3. The temperature was set to 120 ℃ and the remaining process was the same as the 3-step process in comparative example 1.
4. The process was the same as the 4-step process in comparative example 1, resulting in a MIL-Fe-loaded carboxylated polyester fabric having a loading of 154.4 mg/g.
Comparative example 4
1. The process was the same as the 1-step process in comparative example 1.
2. The process was the same as the 2-step process in comparative example 1.
3. The temperature was set to 130 ℃, and the remaining process was the same as the 3-step process in comparative example 1.
4. The process was the same as the 4-step process in comparative example 1, resulting in an MIL-Fe-loaded carboxylated polyester fabric having a loading of 210.3 mg/g.
FIG. 1(a) shows that pits appear on the surface of the polyester fiber after the carboxylation modification treatment. After the MIL-Fe is loaded on the surface of the carboxylic acid polyester fiber, the surface of the carboxylic acid polyester fiber is covered by irregular solid particles, which is caused by the fact that a uniform MIL-Fe film is generated on the surface of the carboxylic acid polyester fiber. As is apparent from fig. 2, the color of the MIL-Fe-supported carboxylated polyester fabric processed using the high temperature and high pressure process in example 3 of the present invention was more uniform than that of the sample prepared using the solvothermal process in comparative example 3 under the same experimental conditions. As can be seen from FIG. 3, the loading amount of MIL-Fe on the surface of the carboxylated polyester fiber increases with the increase of the preparation temperature, and the MIL-Fe loading amount on the surface of the sample prepared by the high-temperature high-pressure method under the same conditions is obviously higher than that of the solvothermal method (comparative examples 1 to 4), which shows that the high-temperature high-pressure method in the invention is more beneficial to the generation and uniform loading and forming of MIL-Fe on the surface of the fiber than the prior art. FIG. 4 shows the effect of MIL-Fe-loaded carboxylated polyester fabrics prepared under different temperature conditions in examples 1-4 and comparative examples 1-4 on the oxidative degradation of reactive red 195. It is noted that the MIL-Fe-loaded carboxylated polyester fabric prepared in example 1 at 100 ℃ has the highest degradation effect on reactive red 195 in the present invention, but the increase of the temperature is not beneficial to further increase of the degradation effect on reactive red 195.
In conclusion, the technical method can effectively combine the organic metal framework and the carboxymethylated polyester fiber, has simple preparation process, easy operation, economy and environmental protection, can not cause secondary pollution, can endow the polyester fiber with the function of degrading dye, can also easily separate the metal organic framework, can not generate a large amount of mud, and develops the application value of the polyester fiber in the field of environmental protection.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several modifications can be made without departing from the inventive concept, and these modifications belong to the protective scope of the invention.
Claims (4)
1. An iron-based organic metal framework MIL-Fe supported carboxylic acid fiber is characterized in that the fiber is reddish brown in appearance and is composed of a crystalline porous material formed by the reaction of iron salt and organic acid and the fiber, wherein the MIL-Fe loading amount is 100 milligrams per gram to 450 milligrams per gram.
2. The iron-based organometallic framework MIL-Fe supported carboxylated fiber of claim 1 wherein the iron-based source can be ferric nitrate, ferric sulfate, or ferric chloride; the carboxylic acid fiber source can be polycarboxylic acid modified cotton fiber, polyacrylic acid grafted polytetrafluoroethylene fiber, polyacrylic acid grafted polypropylene fiber or alkali-treated polyester fiber.
3. The method of claim 1, wherein the iron-based organic metal framework is rapidly formed on the surface of the carboxylated fiber by adopting the following process:
step 1: preparation of a treatment solution: accurately weighing a certain amount of ferric salt and organic carboxylic acid at room temperature, respectively dissolving the ferric salt and the organic carboxylic acid in N, N-dimethylformamide and carrying out ultrasonic treatment for 10 minutes to obtain a treatment solution, wherein the concentration of the ferric salt is 0.05 mol/L to 0.40 mol/L, and the concentration of the organic carboxylic acid is 0.01 mol/L to 0.10 mol/L;
step 2: and (3) a load forming process: putting 50 ml of the treatment solution into a dyeing cup of a high-temperature high-pressure dyeing machine, then putting 1 g of carboxylic fiber into the treatment solution, and reacting for 4 hours under the conditions that the rotating speed is 30 revolutions per minute and the temperature is 100-130 ℃ after sealing treatment so that MIL-Fe is generated on the surface of the carboxylic fiber and is uniformly loaded and formed;
and step 3: and (3) post-treatment: and placing the obtained MIL-Fe-loaded carboxylated fiber into an aqueous solution containing 2.0 g of nonionic detergent per liter, and stirring for 30 minutes at the temperature of 50 ℃ to remove the MIL-Fe which is not firmly loaded on the surface of the fiber.
4. The method of claim 3, wherein the organic carboxylic acid is selected from the group consisting of trimesic acid and terephthalic acid.
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| CN108940374A (en) * | 2018-06-11 | 2018-12-07 | 陕西科技大学 | The preparation method and application of fiber composite film catalyst |
| CN109881483A (en) * | 2019-01-24 | 2019-06-14 | 浙江理工大学 | It is a kind of to utilize metal-organic framework materials functional modification polypropylene/cellulose spunlace non-woven cloth method and its application |
| WO2019175717A1 (en) * | 2018-03-14 | 2019-09-19 | Desiccant Rotors International Private Limited | Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof |
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| WO2019175717A1 (en) * | 2018-03-14 | 2019-09-19 | Desiccant Rotors International Private Limited | Method for in-situ synthesis of metal organic frameworks (mofs), covalent organic frameworks (cofs) and zeolite imidazolate frameworks (zifs), and applications thereof |
| CN108940374A (en) * | 2018-06-11 | 2018-12-07 | 陕西科技大学 | The preparation method and application of fiber composite film catalyst |
| CN109881483A (en) * | 2019-01-24 | 2019-06-14 | 浙江理工大学 | It is a kind of to utilize metal-organic framework materials functional modification polypropylene/cellulose spunlace non-woven cloth method and its application |
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