CN114471472B - Solid-phase microextraction fiber and preparation method and application thereof - Google Patents

Solid-phase microextraction fiber and preparation method and application thereof Download PDF

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CN114471472B
CN114471472B CN202210119843.8A CN202210119843A CN114471472B CN 114471472 B CN114471472 B CN 114471472B CN 202210119843 A CN202210119843 A CN 202210119843A CN 114471472 B CN114471472 B CN 114471472B
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nanotube array
fiber
phase microextraction
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CN114471472A (en
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刘红妹
党世豪
叶保桂
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Lanzhou Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
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    • C02F2101/38—Organic compounds containing nitrogen
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Abstract

The application discloses a solid-phase microextraction fiber and a preparation method and application thereof, relates to the field of materials, and aims to solve the technical problem that the high-efficiency and accurate extraction analysis of non-steroidal drugs in complex water bodies in the prior art is difficult. The preparation method of the solid-phase microextraction fiber comprises the steps of forming a metal oxide nanotube array on the surface of a metal fiber, and carboxylating the metal oxide nanotube array to obtain a carboxylated nanotube array; performing silanization treatment on the carboxylated nanotube array to obtain a silanized nanotube array; coating the silanized nanotube array by using MOFs material to obtain solid-phase microextraction fiber; the metal fibers include one of Ti fibers or Al fibers. The fiber prepared by the preparation method of the solid-phase microextraction fiber is used for efficiently and accurately extracting and analyzing the non-steroidal drugs.

Description

Solid-phase microextraction fiber and preparation method and application thereof
Technical Field
The disclosure relates to the field of materials, and in particular relates to a solid-phase microextraction fiber, and a preparation method and application thereof.
Background
Non-steroidal anti-inflammatory drugs (Nonsteroidal Anti-inflammatory Drugs, NSAIDs) are a class of anti-inflammatory drugs that do not contain a steroidal structure. Because of the large amount of antibiotics, nonsteroidal anti-inflammatory drugs and other drugs, a large amount of water is polluted, so that the human body generates wide drug resistance, and further becomes a serious social problem. In the detection of drugs in environmental water, the detection interference to NSAIDs with extremely low concentration is quite serious due to the presence of a large amount of microorganisms, organic pollutants, salts and inorganic pollutants in the water.
Solid Phase Microextraction (SPME) is a novel efficient and rapid separation technique, but currently, commercial solid phase microextraction fibers cannot realize selective extraction of trace amounts of target substances in complex samples.
Metal-organic frameworks (MOFs) are organic complex materials containing specific functional groups and holes, and can realize selective extraction of target substances. However, MOFs coating materials, when facing detection of complex water bodies, adsorb a large amount of microorganisms and organic compounds, severely affecting the adsorption and enrichment of target substances.
Disclosure of Invention
The application aims to provide a solid-phase microextraction fiber, and a preparation method and application thereof, so as to solve the technical problem that high-efficiency and accurate extraction analysis of non-steroidal drugs is difficult to carry out in complex water bodies.
In order to achieve the above purpose, the application adopts the following technical scheme:
a method for preparing solid phase microextraction fiber comprises forming metal oxide nanotube array on the surface of metal fiber,
carboxylating the metal oxide nanotube array to obtain a carboxylated nanotube array;
performing silanization treatment on the carboxylated nanotube array to obtain a silanized nanotube array;
coating the silanized nanotube array by using MOFs material to obtain solid-phase microextraction fiber;
the metal fibers include one of Ti fibers or Al fibers.
According to at least one embodiment of the present disclosure, the coating of the silanized nanotube array with MOFs material results in a solid-phase microextraction fiber, subjecting the silanized nanotube array to multiple soaking treatments,
the soaking treatment comprises soaking the silanized nanotube array into a metal ion solution and an organic ligand solution, wherein the organic ligand solution comprises an imidazole, pyridine and DMF solution of aromatic polycarboxylic acid and derivatives thereof.
According to at least one embodiment of the present disclosure, in the immersing process, the reaction temperature of immersing the silanized nanotube array into the metal ion solution and the reaction temperature of the organic ligand solution are both 20 ℃ to 60 ℃.
According to at least one embodiment of the present disclosure, the carboxylation treatment is performed on the metal oxide nanotube array to obtain a carboxylated nanotube array, wherein the carboxylated solution is an aqueous solution of an organic weak acid, and the concentration of the aqueous solution of the organic weak acid is 0.005mol/L to 0.05mol/L.
According to at least one embodiment of the present disclosure, the carboxylated nanotube array is subjected to a silylation treatment to obtain a silylated nanotube array, the silylated solution is a toluene solution of a silylating agent, the silylating agent includes one or more of carboxyethyl silanetriol sodium salt, 1- (dimethyl-n-propyl silyl) imidazole, aniline methyltriethoxysilane, aminopropyl triethoxysilane, or aminopropyl triethoxysilane, and a volume ratio of the silylating agent to toluene is (5-15): (85-95).
According to at least one embodiment of the present disclosure, the forming of the metal oxide nanotube array on the surface of the metal fiber includes performing at least one anodic oxidation with the metal fiber as an anode in an electrolyte containing a pore-forming agent, the anodic oxidation having a reaction voltage of 10V to 100V, and/or,
the reaction temperature is 10 ℃ to 50 ℃, and/or,
the reaction time is 10 min-60 min.
According to at least one embodiment of the present disclosure, the metal fibers have a diameter of 100 μm to 300 μm; and/or the number of the groups of groups,
the pore-forming agent comprises one or more of ammonium fluoride and hydrofluoric acid; and/or the number of the groups of groups,
the electrolyte comprises an organic weak electrolyte comprising one or more of ethylene glycol, dimethyl sulfoxide and DMF.
According to at least one embodiment of the present disclosure, the mass ratio of the porogen to the electrolyte is (0.2-1): 100.
compared with the prior art, the preparation method of the solid-phase microextraction fiber provided by the application has the advantages that firstly, the oxide layer of the nanotube array of the metal oxide is formed on the surface of the titanium or aluminum metal fiber, the nanotube array of the metal oxide is subjected to functionalization treatment to obtain the nanotube array of the silanized metal oxide, and silane groups are introduced into molecules of the nanotubes of the metal oxide, so that the number of reactive sites containing active hydrogen is reduced due to the substitution of active hydrogen, a large number of groups which are convenient for MOFs to grow are formed on the inner wall of the nanotubes, the nucleation speed of MOFs molecules is higher than the growth speed of MOFs, and finally, MOFs materials in the obtained metal oxide nanotubes uniformly grow in a small-particle size mode, so that the extraction specific surface area of MOFs is improved. By compounding a large amount of MOFs materials on the inner wall of the nano tube array of the silanized metal oxide, on one hand, MOFS molecules are dispersed on the inner wall of the nano tube array of the metal oxide, so that the specific surface area and the extraction capacity are greatly improved; on the other hand, the adjustment of the diameter of the nanotube array of the metal oxide is realized by controlling the conditions in the process of forming the nanotube array of the metal oxide on the surface of the metal fiber and controlling the conditions in the process of coating the silanized nanotube array by using MOFs materials, so that a large number of macromolecular interferents (such as microorganisms and the like) in a water body can be limited to enter the nanotube array of the metal oxide to occupy adsorption points, the screening and the extraction on the molecular size are realized firstly, and then the high-efficiency and selective extraction of the nonsteroidal drugs in the complex water body are realized by utilizing the combined action of holes and functional groups of the MOFs structure.
The application also provides a solid-phase microextraction fiber, which is prepared by adopting the preparation method of the solid-phase microextraction fiber.
Compared with the prior art, the solid-phase microextraction fiber has the following advantages:
the solid-phase microextraction fiber has the same advantages as the preparation method of the solid-phase microextraction fiber, and is not described in detail herein.
The application also provides application of the solid phase microextraction fiber in extracting non-steroidal drugs in complex water bodies.
Compared with the prior art, the application of the solid phase microextraction fiber in extracting the non-steroidal drugs in the complex water body has the following advantages:
the application of the solid-phase microextraction fiber in extracting the non-steroidal drugs in the complex water body has the advantages which are the same as those of the preparation method of the solid-phase microextraction fiber, and the detailed description is omitted.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
FIG. 1 is a TiO of the present disclosure 2 Morphology of nanotube array composite MOFs. Wherein a is TiO 2 The shape of the nanotube array coating; b is TiO 2 Nanotube array/MOFs composite coating morphology.
Fig. 2 is a gas chromatogram of a solid phase microextraction fiber and a polypropylene coated solid phase microextraction fiber of an embodiment of the present disclosure after extraction.
Fig. 3 is a flow chart of a method of preparing a solid phase microextraction fiber of the present disclosure.
Detailed Description
The present disclosure is described in further detail below with reference to the drawings and the embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant content and not limiting of the present disclosure. It should be further noted that, for convenience of description, only a portion relevant to the present disclosure is shown in the drawings.
In addition, embodiments of the present disclosure and features of the embodiments may be combined with each other without conflict. The present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
The core of the solid phase microextraction technology is SPME coating, which has the requirements of strong enrichment capacity and good target selectivity. However, the main problems of the various application coatings at present are: the extraction selectivity is poor. The common selective extraction mainly uses the principle of similar compatibility between the extraction material and the target, hydrogen bonding, pi-pi, pi-cation, van der Waals forces and the like, and the specificity of the forces is poor. The organic polymer and the organic complex containing specific functional groups and holes can accurately select the extraction target molecules, but the preparation process of the organic polymer and the organic complex still has the problems of template molecule residue and leakage. These problems affect the detection of objects in complex matrices with high precision and accuracy. The solid phase microextraction fiber used in commercial use at present can not realize the selective extraction of trace target substances in complex samples.
The existing MOFs material is an organic complex material containing specific functional groups and holes, and can form ideal holes and functional group structures suitable for the molecular size and characteristics of a target object, so that the purpose of exclusive selective extraction of the target object is achieved. However, the pure MOFs coating material has larger grain size, limited specific surface area and smaller extraction capacity, and complex water contains a large amount of microorganisms and organic compounds which have a plurality of active functional groups and are easily adsorbed on the extraction fiber coating to occupy a large number of adsorption points, so that the adsorption and enrichment of target objects are seriously affected.
In view of the above problems, an embodiment of the present application provides a method for preparing a solid-phase microextraction fiber, including forming a metal oxide nanotube array on a surface of a metal fiber, and carboxylating the metal oxide nanotube array to obtain a carboxylated nanotube array; performing silanization treatment on the carboxylated nanotube array to obtain a silanized nanotube array; coating the silanized nanotube array by using MOFs material to obtain solid-phase microextraction fiber; the metal fibers include one of Ti fibers or Al fibers.
Illustratively, the titanium metal fiber forms TiO on its surface 2 Nanotube array and in TiO 2 MOFs are attached to the inner wall of the nanotube array to form TiO 2 The nanotube array loads MOFs molecular composite nano-structure. The hole and functional group screening function of MOFs structure can realize selective extraction of non-steroidal drugs, while the diameter of the nano structure of the nanotube array can limit a large number of macromolecular interferents (such as microorganisms and the like) in water body to enter the nanoThe rice tube occupies adsorption points, so that the selective extraction is firstly carried out from the molecular size, and then the selective extraction is carried out by utilizing the combined action of the cavity and the functional group of the MOFs structure, and the selective extraction of the non-steroidal drugs in the complex water body is realized, thereby carrying out efficient and accurate extraction analysis on the non-steroidal drugs in the environmental water sample. Alternatively, the surface of the aluminum oxide nano tube array can be formed by Al fiber, so that the MOFs molecular-loaded composite nano structure of the aluminum oxide nano tube array is formed.
In some embodiments, carboxylation of the metal oxide nanotube array may form activated hydrogen on the inner walls of the nanotube array, providing sites for siloxane groups or feature groups of subsequent silylation. The siloxane groups of the silylating agent hydrolyze to form Si-OH, which dehydrates with Ti-OH or Al-OH on the nanotube surface, thereby imparting different silylating agent-specific groups to the nanotubes. The silanization treatment enables a large number of groups which are convenient for MOFs growth to be formed on the inner wall of the nanotube, so that the nucleation speed of MOFs molecules is larger than the growth speed of MOFs molecules, and finally the MOFs material in the nanotube is uniformly grown in a small particle size mode, so that the extraction specific surface area of the MOFs material is improved. The common selective extraction coating in the prior art mainly utilizes the similar compatibility principle, hydrogen bond action, pi-pi, pi-cation action, van der Waals force and the like between an extraction material and a target object, and the specificity of the acting force is poor. The organic polymer and the organic complex containing specific functional groups and holes can accurately select the extraction target molecules, but the preparation process of the organic polymer and the organic complex still has the problems of template molecule residue and leakage. The MOFs coating material is simply used, and has the advantages of larger grain size, limited specific surface area and smaller extraction capacity, and a large number of microorganisms and organic compounds which have a plurality of active functional groups are contained in complex water bodies, so that the MOFs coating material can be easily adsorbed on an extraction fiber coating, occupy a large number of adsorption points, and seriously influence the adsorption and enrichment of target objects. Therefore, the nanotube array loaded MOFs molecular composite nanostructure provided by the embodiment of the application has the advantages that the preparation method is simple, the nanotube structure is adopted to limit the entry of macromolecular interferents, the screening and extraction on the molecular size are realized, and the problem that the target is not easy to adsorb and enrich is solved.
In certain embodiments, solid phase microextraction fibers are obtained by subjecting the silanized nanotube array to multiple soaking treatments while MOFs are coated on the silanized nanotube array. The soaking treatment includes soaking the silanized nanotube array in a solution containing metal ions for a period of time and then placing the nanotube array in an organic ligand solution for a period of time. Soaking treatment, namely immersing the nanotube array into a metal ion solution and an organic ligand solution, and sequentially circulating for a plurality of times to obtain the metal oxide nanotube array/MOFs composite SPME fiber. Namely, a step-by-step assembly method is adopted to assemble the MOFs coating layer by layer, and the cycle times of soaking treatment can control the integral pore diameter of the composite SPME fiber. The number of circulation times is selected according to different extraction environments, so that the circulation times can be reduced when the influence of macromolecules in the water body is large, and conversely, the circulation times can be increased when the volume of interferents in the water body is small, and the rejection of the interferents is improved. Please refer to fig. 1, wherein a of fig. 1 is TiO without MOFs coating 2 Morphology of the nanotube array, b of FIG. 1 is TiO for MOFs coatings 2 Morphology of the nanotube array. TiO before coating 2 The nanotube array has a uniform nanotube diameter, the tube wall is thin, after MOFs are compounded, some accumulation is obviously generated at the nanotube orifice, and the tube diameter is also obviously reduced. It is known that the tube diameter of the composite material is effectively controlled by controlling the preparation conditions, such as the number of cycles of the coating, optionally 10-40 times, and optionally 10-30 times, so as to screen from the molecular size, thereby obtaining the selective extraction of the target.
Further, the metal ion aqueous solution used in the above-mentioned soaking treatment may be any metal ion which forms a stable complex with an organic ligand, and the metal ion is exemplified by Zn 2+ 、Cu 2+ 、Cr 3+ 、Co 2+ 、Al 3+ Etc., the concentration of the metal ion is 0.05mol/L to 0.5mol/L, optionally 0.1mol/L to 0.3 mol-L. The organic ligand solution used in the above soaking treatment is an N, N-Dimethylformamide (DMF) solution, the organic ligand is a reagent capable of forming multiple actions with a nonsteroidal drug, such as Lewis acid base action, pi-pi action, etc., and the organic ligand includes imidazole, pyridine, aromatic polycarboxylic acid and derivatives thereof, etc., and the concentration of DMF solution of the organic ligand is 0.2mol/L to 2mol/L, alternatively 0.5mol/L to 1mol/L.
Considering the influence of soaking treatment on the thickness of MOFs material, in order to prevent the phenomenon that the MOFs material grows too fast in the nanotubes to cause the nanotube blockage, and to facilitate the control of the thickness of the MOFs material in the nanotubes, MOFs are grown layer by layer under mild conditions, and the reaction temperature and the reaction time are matched with each other. Illustratively, the reaction temperature in the soaking treatment is 20-60 ℃, optionally 35-50 ℃, and the reaction time of the nanotube in the metal ion solution and the organic ligand solution in the soaking treatment is 10-30 min, optionally 15-25 min. The diameter of the MOFs molecular composite nano structure loaded by the nanotube array can be regulated and controlled through the reaction temperature and the reaction time.
In some embodiments, when the metal oxide nanotube array is carboxylated, in order to form Ti-OH or Al-OH on the surface of the nanotube, the subsequent silylation of the nanotube is facilitated, and the carboxylation is performed on the nanotube first. Since the nanostructure has a higher reactivity than the bulk material, in order to prevent the nanotubes from being severely corroded by strong inorganic acid to cause morphology damage, the nanotubes are carboxylated by aqueous solution of weak organic acid, illustratively acetic acid, succinic acid or citric acid, etc., while the weak organic acid is also used at a lower concentration, illustratively 0.005mol/L to 0.05mol/L, alternatively 0.01mol/L to 0.03mol/L. The above carboxylation treatment is carried out in a milder manner, for example, at a temperature of 20 to 80 ℃, optionally 40 to 60 ℃ for a period of 0.5 to 3 hours, optionally 1 to 2 hours.
In order to increase the extraction specific surface area of MOFs materials, the nanotubes need to be silanized. Illustratively, the silylated solution is a toluene solution of a silylating agent comprising one or more of carboxyethyl silane triol sodium salt, 1- (dimethyl-n-propyl silyl) imidazole, aniline methyl triethoxysilane, aminopropyl triethoxysilane, or aminopropyl triethoxysilane. The silylating agent has similar or identical functional groups as the ligands forming the MOFs material, facilitating subsequent coordination of the metal ions. The siloxane groups of the silylation agent hydrolyze to form Si-OH groups, which react with Ti-OH or Al-OH on the nanotube surface in a dehydration reaction, thereby allowing the nanotube to carry characteristic groups of different silylation agents. Therefore, a large number of groups which are convenient for MOFs growth are formed on the inner wall of the nanotube, so that the nucleation speed of MOFs molecules is larger than the growth speed of MOFs molecules, and finally the MOFs material in the nanotube is smaller in particle size and uniformly grows, so that the extraction specific surface area of the MOFs material is increased. Illustratively, the volume ratio of silylating agent to toluene is (5-15): (85-95) when the volume ratio of the silylating agent to toluene is within this range, it is ensured that sufficient groups are formed on the inner wall of the nanotube to facilitate MOFs growth. Since the nanotubes are silanized, the temperature and time of the silanization are also carried out under milder conditions, for example, 20-80 ℃, optionally 40-60 ℃, 3-10 h, optionally 5-7 h, in order to prevent damage to the morphology of the nanotubes.
Compared with the preparation method for directly growing MOFs on the nanotubes which are not subjected to the silanization treatment, the MOFs obtained by the method can enter the interior of the nanotubes better and realize uniform growth of small particles. Compared with a hydrothermal method in the prior art, the preparation process of the embodiment of the application is milder and controllable, is convenient for carrying out secondary control and adjustment on the pipe diameter of the MOFs molecular-loaded composite nanostructure of the metal oxide nanotube array according to the volume and the content of the interferents in the water body, and is beneficial to realizing the selective extraction of the nonsteroidal drugs.
The above-mentioned methods for preparing the metal oxide nanotube array are various, and the metal oxide nanotube array provided by the embodiment of the application is prepared by adopting the following methods:
the method for forming the metal oxide nanotube array on the surface of the metal fiber comprises the steps of taking the metal fiber as an anode, placing the metal fiber into electrolyte containing a pore-forming agent for at least one time of anodic oxidation, wherein the reaction voltage of the anodic oxidation is 10-100V, the reaction temperature is 10-50 ℃, and the reaction time is 10-60 min. The actual number of anodic oxidation times for forming the metal oxide nanotube array on the surface of the metal fiber by adopting the anodic oxidation method is carried out according to the morphology of the nanotubes, and the pore diameter of the nanotubes formed after one anodic oxidation is easy to block and the phenomenon that part of the nanotubes lodge occurs, and the anodic oxidation is carried out for two or more times under the same or different conditions as the one anodic oxidation after the ultrasonic stripping of the nanotube array from the metal fiber in deionized water, wherein the number of the anodic oxidation times is 1-3 times, optionally 2 times. Because of the finer diameter of the metal fibers, a greater number of anodic oxidation results in complete dissolution loss of the metal fibers. It will be appreciated that in the anodic oxidation process, the cathode material used may be other auxiliary electrodes, such as graphite, and is not particularly limited in some embodiments.
In some embodiments, after the nanotube array has been anodized, the metal fibers with the nanotube array are calcined at an elevated temperature in order to remove residual species after the anodization and activate the lattice of the nanotubes, facilitating further reactions of the nanotube array. Illustratively, the calcination temperature is 350 ℃ to 500 ℃, alternatively 400 ℃ to 450 ℃, when the calcination temperature is too high, the nanotubes are sintered to destroy the morphology of the nanotubes, and when the calcination temperature is too low, the purposes of cleaning and activating the nanotubes cannot be achieved. Optionally, the high temperature calcination time is 30 min-90 min.
The diameter of the metal fiber is, for example, 100 μm to 300 μm, and the purity of the Ti fiber and the Al fiber is 99.9%. In order to obtain the nano-tubular structure of the metal oxide, a porogen is required to be added to the electrolyte, and illustratively, the porogen comprises one or more of ammonium fluoride and hydrofluoric acid; compared with the prior art, the pore-forming agent required by the nano tube of the embodiment of the applicationIs different from other conventional pore forming agents, for example, ti metal, F is required - Etching titanium oxide formed by ions, wherein the reaction formula is TiO 2 +6F - +H + ＝TiF 6 2- +2H 2 O, therefore the porogen also needs to have some acidity. When the metal fiber is thinner, the etching speed is not easy to control in consideration of the too strong acidity of hydrofluoric acid, and the pore-forming agent is ammonium fluoride; hydrofluoric acid may also be selected as the porogen when the metal fibers are relatively coarse.
In view of the relatively small diameter of the metal fiber matrix, the reaction conditions need to be easily controlled during the oxidation thereof, and the above-mentioned electrolyte includes, for example, an organic weak electrolyte including one or more of ethylene glycol, dimethyl sulfoxide and DMF. Compared with inorganic strong electrolyte, the organic weak electrolyte has a certain inhibition effect on electrochemical reaction in the oxidation process, and meanwhile, the strength, the conductivity and the anodic oxidation speed of the organic weak electrolyte are convenient to control through conditions such as temperature, voltage and the like, so that the organic weak electrolyte is more suitable for the oxidation process of a metal fiber matrix.
Illustratively, the mass ratio of the pore-forming agent to the electrolyte is (0.2-1): 100, when the mass ratio of the pore-forming agent to the electrolyte is controlled in the range, excessive use of the pore-forming agent does not cause excessive etching of the metal fiber, so that the metal fiber is completely dissolved and broken. Meanwhile, the metal oxide nanotubes cannot be prepared due to too little pore-forming agent.
In order to control the aperture of the nanotube, the reaction voltage of the anodic oxidation is 10V-100V, the reaction temperature is 10-50 ℃, and the reaction time is 10-60 min. The pore size of the nanotubes increases with increasing voltage, but too much voltage can cause damage to the morphology of the nanotubes and even complete dissolution of the wires, for example, a reaction voltage of 40V to 80V. The reaction temperature and reaction time of anodic oxidation can control the growth speed of the nano tube, thereby changing the length of the nano tube, and although the long nano tube can accommodate more MOFs and improve the extraction capacity, the metal wire is easy to dissolve and break due to the thin diameter of the metal wire. Illustratively, the reaction temperature of the anodic oxidation is 10 ℃ to 30 ℃ and the reaction time is 20min to 40min. When the reaction temperature and the reaction time of the anodic oxidation are within this range, the produced nanotubes are optimal. It will be appreciated that the reaction conditions for one anodic oxidation may be the same as or different from the reaction conditions for multiple anodic oxidation.
The anodic oxidation reaction conditions and the multiple coating can uniformly control the diameter of the nanotube array within the range of tens to hundreds of nanometers, so that nanotubes with different diameters can be prepared according to the size of macromolecules in a water body, and the aim of screening and extracting from the molecular size is fulfilled.
Referring to fig. 3, the method for preparing the solid-phase microextraction fiber includes the steps of:
step S100: and forming a metal oxide nanotube array on the surface of the metal fiber.
Specifically, taking a Ti metal fiber carrier as an anode and graphite as a cathode, putting the anode and the cathode into an electrolytic solution containing a pore-forming agent, and performing primary anodic oxidation under certain reaction voltage, temperature and reaction time conditions; then the nano tube array of the primary anodic oxidation is peeled off in deionized water in an ultrasonic way, and then the secondary anodic oxidation is carried out under the same preparation condition, and finally the fiber is calcined at high temperature.
Step S200: and (3) carboxylating and silanizing the metal oxide nanotube array.
Specifically, the nanotube array is put into an organic acid solution, subjected to hydroxylation treatment at a certain temperature, then rinsed with a large amount of deionized water and dried; and then hydroxylating the TiO 2 The nanotube array is soaked in a silanization reagent solution, silanization treatment is carried out at a certain temperature, and then a large amount of deionized water is used for washing and airing.
Step S300: the silanized nanotube arrays were coated with MOFs material.
Silanized TiO 2 The nanotube array is immersed in a solution containing metal ions for a period of time and then placed in an organic ligand solution for a period of time. Sequentially and circularly processing to obtain TiO 2 Nanometer scaleTube arrays/MOFs composite SPME fibers.
Examples of several solid phase microextraction fibers are given below.
Example 1
(1) Taking Ti metal fiber as an anode and graphite as a cathode, and performing anodic oxidation in a mixed solution of ammonium fluoride aqueous solution with the concentration of 0.03mol/L and ethylene glycol electrolyte, wherein the mass ratio of the ammonium fluoride to the ethylene glycol is 1:100, and performing anodic oxidation for 40min under the conditions of the reaction temperature of 70 ℃ and the reaction voltage of 10V. Ultrasonically stripping the Ti metal fiber subjected to anodic oxidation in deionized water;
(2) Under the same anodic oxidation condition, carrying out secondary anodic oxidation on the stripped Ti metal fiber, and calcining the Ti metal fiber after secondary anodic oxidation at 350 ℃ for 90min;
(3) Soaking the calcined Ti metal fiber in 0.005mol/L acetic acid water solution for 2 hours at the soaking temperature of 60 ℃, washing with deionized water and airing;
(4) Soaking the Ti metal fiber after soaking in 1- (dimethyl n-propyl silyl) imidazole for 1h at the soaking temperature of 60 ℃, washing with deionized water and airing;
(5) Will contain silanized TiO 2 Soaking the fiber of the nanotube array into Zn with the concentration of 0.05mol/L 2+ In an ionic aqueous solution, the reaction temperature is 30 ℃, after 30min, the solution is taken out, and unreacted metal ions are removed by using a solvent;
(6) The silanized TiO obtained in the step (5) is added 2 Immersing the fibers of the nanotube array into DMF solution with the concentration of 0.2mol/L pyridine, and taking out after 30 minutes at the reaction temperature of 30 ℃;
(7) Repeating the step (5) and the step (6) for 20 times.
Example 2
(1) Taking Ti metal fiber as an anode and graphite as a cathode, and performing anodic oxidation in a mixed solution of ammonium fluoride aqueous solution with the concentration of 0.1mol/L and dimethyl sulfoxide electrolyte, wherein the mass ratio of the ammonium fluoride to the dimethyl sulfoxide is 0.5:100, and performing anodic oxidation for 20min under the conditions of the reaction temperature of 50 ℃ and the reaction voltage of 30V. Ultrasonically stripping the Ti metal fiber subjected to anodic oxidation in deionized water;
(2) Under the same anodic oxidation condition, carrying out secondary anodic oxidation on the stripped Ti metal fiber, and calcining the Ti metal fiber after secondary anodic oxidation at 400 ℃ for 60min;
(3) Soaking the calcined Ti metal fiber in succinic acid aqueous solution with the concentration of 0.01mol/L for 4 hours at the soaking temperature of 40 ℃, flushing with deionized water and airing;
(4) Soaking the Ti metal fiber after soaking in aniline methyltriethoxysilane for 2 hours at the soaking temperature of 40 ℃, washing with deionized water and airing;
(5) Will contain silanized TiO 2 Soaking the fiber of the nanotube array into Al with the concentration of 0.2mol/L 2+ In an ionic aqueous solution, the reaction temperature is 40 ℃, after 20min, the solution is taken out, and unreacted metal ions are removed by using a solvent;
(6) The silanized TiO obtained in the step (5) is added 2 Immersing the fibers of the nanotube array into DMF solution with the concentration of 0.8mol/L of amino terephthalic acid, and taking out after 20min at the reaction temperature of 40 ℃;
(7) Repeating the step (5) and the step (6) for 30 times.
Example 3
(1) Taking Ti metal fiber as an anode and graphite as a cathode, and performing anodic oxidation in a mixed solution of ammonium fluoride aqueous solution with the concentration of 0.07mol/L and DMF electrolyte, wherein the mass ratio of the ammonium fluoride to the DMF is 0.5:100, and performing anodic oxidation for 10min under the conditions of the reaction temperature of 80 ℃ and the reaction voltage of 60V. Ultrasonically stripping the Ti metal fiber subjected to anodic oxidation in deionized water;
(2) Under the same anodic oxidation condition, carrying out secondary anodic oxidation on the stripped Ti metal fiber, and calcining the Ti metal fiber after secondary anodic oxidation at 450 ℃ for 30min;
(3) Soaking the calcined Ti metal fiber in citric acid aqueous solution with the concentration of 0.02mol/L for 6 hours at the soaking temperature of 20 ℃, flushing with deionized water and airing;
(4) Soaking the Ti metal fiber after soaking in aniline methyltriethoxysilane for 3 hours at 20 ℃, washing with deionized water and airing;
(5) Will contain silanized TiO 2 Soaking the fiber of the nanotube array into Cr with the concentration of 0.5mol/L 2+ In an ionic aqueous solution, the reaction temperature is 60 ℃, the solution is taken out after 10min, and unreacted metal ions are removed by using a solvent;
(6) The silanized TiO obtained in the step (5) is added 2 Immersing the fibers of the nanotube array into a DMF solution with the concentration of 2mol/L pyridine, and taking out after 10min at the reaction temperature of 60 ℃;
(7) Repeating the step (5) and the step (6) for 30 times.
Example 4
(1) Taking Al metal fiber as an anode and graphite as a cathode, and performing anodic oxidation in a mixed solution of ammonium fluoride aqueous solution with the concentration of 0.03mol/L and ethylene glycol electrolyte, wherein the mass ratio of the ammonium fluoride to the ethylene glycol is 0.2:100, and performing anodic oxidation for 40min under the conditions of the reaction temperature of 70 ℃ and the reaction voltage of 10V. Ultrasonically stripping the Al metal fiber subjected to anodic oxidation in deionized water;
(2) Under the same anodic oxidation condition, carrying out secondary anodic oxidation on the stripped Al metal fiber, and calcining the Al metal fiber after secondary anodic oxidation at 350 ℃ for 90min;
(3) Immersing the calcined Al metal fiber in 0.005mol/L acetic acid aqueous solution for 2 hours at 60 ℃, washing with deionized water and airing;
(4) Soaking the Al metal fiber after soaking in 1- (dimethyl n-propyl silyl) imidazole for 1h at a soaking temperature of 60 ℃, washing with deionized water and airing;
(5) Will contain silanized Al 2 O 3 Soaking the fiber of the nanotube array into Zn with the concentration of 0.05mol/L 2+ In an ionic aqueous solution, the reaction temperature is 30 ℃, after 30min, the solution is taken out, and unreacted metal ions are removed by using a solvent;
(6) The silanized TiO obtained in the step (5) is added 2 Immersing the fibers of the nanotube array into DMF solution with the concentration of 0.2mol/L pyridine, and taking out after 30 minutes at the reaction temperature of 30 ℃;
(7) Repeating the step (5) and the step (6) for 20 times.
The solid phase microextraction fiber gas chromatography prepared by the embodiment of the application is used for extracting two non-steroidal drugs, such as ibuprofen and diclofenac sodium, in a yellow river water sample. FIG. 2 shows the comparison of the chromatograms of the solid-phase microextraction fiber prepared by the embodiment of the application and the commercial acrylic acid coating solid-phase microextraction fiber for extracting a yellow river water sample (marked with 0.003 mug/L), wherein the solid-phase microextraction fiber prepared by the embodiment of the application has obvious chromatographic peaks for the extraction of two targets, and the baseline of the integral chromatogram is more stable and has few impurity peaks; commercial fibers, however, have poor extractability for both targets and show few chromatographic peaks. The solid phase microextraction fiber has excellent extraction selectivity. Other extraction performance metrics were as follows: through extraction concentration range of 0.001 mu g L -1 ～200μg L -1 Linearity was tested for two common aqueous solutions of non-steroidal drugs. All analytes showed good linearity with measured values (R) ranging from 0.9975 to 0.9989. The detection limits of the ibuprofen and the diclofenac sodium in the embodiment of the application are 0.0005 mu g L -1 Limit of quantification [ LOQs (S/N=10)]Are all 0.002 mu g L -1 . The reproducibility of the metal fibers of the examples of the present application was evaluated in parallel three times by continuous extraction experiments, with RSDs of less than 4.44%, while the daily reproducibility and the daytime reproducibility were respectively less than 5.11%.
In conclusion, the solid-phase microextraction fiber prepared by the preparation method of the solid-phase microextraction fiber provided by the embodiment of the application can realize efficient and selective extraction of the nonsteroidal drugs in the complex water body.
The embodiment of the application also provides a solid-phase microextraction fiber, which is prepared by adopting the preparation method of the solid-phase microextraction fiber.
Compared with the prior art, the solid-phase microextraction fiber provided by the embodiment of the application has the same beneficial effects as the solid-phase microextraction fiber preparation method provided by the embodiment, and is not repeated herein.
The embodiment of the application also provides application of the solid phase microextraction fiber in extracting non-steroidal drugs in complex water bodies.
Compared with the prior art, the application of the solid-phase microextraction fiber provided by the embodiment of the application has the same beneficial effects as the preparation method of the solid-phase microextraction fiber provided by the embodiment, and the description is omitted here.
In the description of the present specification, reference to the terms "one embodiment/manner," "some embodiments/manner," "example," "a particular example," "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/manner or example is included in at least one embodiment/manner or example of the application. In this specification, the schematic representations of the above terms are not necessarily for the same embodiment/manner or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/modes or examples described in this specification and the features of the various embodiments/modes or examples can be combined and combined by persons skilled in the art without contradiction.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
It will be appreciated by those skilled in the art that the above-described embodiments are merely for clarity of illustration of the disclosure, and are not intended to limit the scope of the disclosure. Other variations or modifications will be apparent to persons skilled in the art from the foregoing disclosure, and such variations or modifications are intended to be within the scope of the present disclosure.

Claims (7)

1. The preparation method of the solid-phase microextraction fiber is characterized by comprising the steps of taking a metal fiber as an anode, placing the metal fiber into an electrolyte containing a pore-forming agent for at least one anodic oxidation, and forming a metal oxide nanotube array on the surface of the metal fiber; the reaction voltage of the anodic oxidation is 10V-100V, and/or,
the reaction temperature is 10 ℃ to 50 ℃, and/or,
the reaction time is 10 min-60 min;
carboxylating the metal oxide nanotube array to obtain a carboxylated nanotube array;
performing silanization treatment on the carboxylated nanotube array to obtain a silanized nanotube array;
coating the silanized nanotube array by using MOFs material to obtain solid-phase microextraction fiber, wherein the process comprises the steps of carrying out multiple soaking treatment on the silanized nanotube array:
the soaking treatment comprises the steps of soaking the silanized nanotube array into a solution containing metal ions for a period of time, and then putting the nanotube array into an organic ligand solution for a period of time;
the soaking treatment is sequentially circulated for 10 to 40 times;
in the soaking treatment, the silylated nanotube array is soaked to the reaction temperature of the metal ion solution and the reaction temperature of the organic ligand solution at 20-60 ℃;
the organic ligand solution comprises DMF solution of imidazoles, pyridines and aromatic polycarboxylic acid and derivatives thereof;
the metal ion is Zn 2+ 、Cu 2+ 、Cr 3+ 、Co 2+ Or Al 3+ One of the following;
the metal fibers include one of Ti fibers or Al fibers.
2. The method for preparing solid-phase microextraction fiber according to claim 1, wherein the carboxylation treatment is performed on the metal oxide nanotube array to obtain a carboxylated nanotube array, the carboxylated solution is an aqueous solution of an organic weak acid, and the concentration of the aqueous solution of the organic weak acid is 0.005 mol/L-0.05 mol/L.
3. The method for preparing solid-phase microextraction fiber according to claim 1, wherein the carboxylated nanotube array is subjected to silanization treatment to obtain a silanized nanotube array, the silanized solution is toluene solution of a silanization reagent, the silanization reagent comprises one or more of carboxyethyl silanetriol sodium salt, 1- (dimethyl-n-propylsilyl) imidazole, aniline methyltriethoxysilane or aminopropyl triethoxysilane, and the volume ratio of the silanization reagent to toluene is (5-15): (85-95).
4. The method for producing solid phase microextraction fiber according to claim 1, wherein the diameter of the metal fiber is 100 μm to 300 μm; and/or the number of the groups of groups,
the pore-forming agent comprises one or more of ammonium fluoride and hydrofluoric acid; and/or the number of the groups of groups,
the electrolyte comprises an organic weak electrolyte comprising one or more of ethylene glycol, dimethyl sulfoxide and DMF.
5. The method for preparing solid-phase microextraction fiber according to claim 1, wherein the mass ratio of the pore-forming agent to the electrolyte is (0.2-1): 100.
6. a solid phase microextraction fiber prepared by the method of any one of claims 1 to 5.
7. The use of the solid phase microextraction fiber of claim 6 for extracting non-steroidal drugs in complex water bodies.
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