阅读说明：本技术 一种柔性铝镁复合氧化物纳米纤维膜及其制备方法与应用 (A kind of flexibility magnalium composite oxides nano fibrous membrane and the preparation method and application thereof ) 是由 章莉娟 杨谦 庾明茂 黄悦 于 2019-08-13 设计创作，主要内容包括：本发明属于无机纳米纤维材料技术领域,公开了一种柔性铝镁复合氧化物纳米纤维膜及其制备方法与在环境治理修复领域中的应用,特别适用于重金属吸附领域。本发明的柔性铝镁复合氧化物纳米纤维膜以铝源、镁源为原料,钇盐为掺杂剂,酸为水解催化剂,聚乙烯吡咯烷酮和聚氧化乙烯的至少一种作为纺丝助剂,在溶剂体系中通过溶胶-凝胶法结合静电纺丝技术得到干凝胶纤维,再经分段煅烧制得。本发明通过溶胶-凝胶法结合静电纺丝技术制备得到的柔性铝镁复合氧化物纳米纤维,具有大比表面积、高孔隙率,且力学性能优异、柔韧性好,其作为吸附材料具有吸附率速率快,去除率高等特点,且避免了粉末吸附剂易团聚、难回收等缺点,可应用于环境治理修复领域。(The invention belongs to inorganic nano-fiber field of material technology, a kind of flexible magnalium composite oxides nano fibrous membrane and preparation method thereof and the application in environmental improvement reparation field are disclosed, especially suitable for heavy metal adsorption field.Flexible magnalium composite oxides nano fibrous membrane of the invention is using silicon source, magnesium source as raw material, yttrium salt is dopant, acid is hydrolyst, the at least one of polyvinylpyrrolidone and polyethylene glycol oxide is as spin finish aid, xerogel fiber is obtained by sol-gel method combination electrostatic spinning technique in dicyandiamide solution, then segmented calcining is made.The flexible magnalium composite oxides nanofiber that the present invention is prepared by sol-gel method combination electrostatic spinning technique, with bigger serface, high porosity, and excellent in mechanical performance, flexibility are good, it has adsorption rate rate fast as adsorbent material, the features such as removal rate is high, and the disadvantages of avoiding powder sorbent easy to reunite, difficult recycling, it can be applied to environmental improvement and repair field.)

1. a kind of flexibility magnalium composite oxides nano fibrous membrane, it is characterised in that using silicon source, magnesium source as raw material, yttrium salt is doping Agent, acid are hydrolyst, and at least one of polyvinylpyrrolidone and polyethylene glycol oxide is as spin finish aid, in dicyandiamide solution In xerogel fiber obtained by sol-gel method combination electrostatic spinning technique, then segmented calcining is made.

2. flexibility magnalium composite oxides nano fibrous membrane according to claim 1, it is characterised in that: the magnesium source and aluminium The molar ratio in source is 1:9-3:7；The molar ratio of the dopant and silicon source is 1:10-1:50.

3. flexibility magnalium composite oxides nano fibrous membrane according to claim 1, it is characterised in that: the silicon source is Water-soluble aluminum salt；The magnesium source is water-soluble magnesium salt；The yttrium salt includes at least one of yttrium nitrate, yttrium chloride.

4. flexibility magnalium composite oxides nano fibrous membrane according to claim 1, it is characterised in that: the electrostatic spinning Process conditions are as follows: voltage 15-25KV；Spinning solution sprays rate: 0.5-1.2mL/h；Receive distance: 12-20cm；Environment temperature Degree: 20-30 DEG C；Ambient humidity: 40-50%.

5. flexibility magnalium composite oxides nano fibrous membrane according to claim 1, it is characterised in that: the calcining is Divide two-section calcining, is included in 250-300 DEG C of calcining 1-2h, then be warming up to 600-800 DEG C of calcining 1-4h.

6. flexibility magnalium composite oxides nano fibrous membrane according to claim 1, it is characterised in that: the calcining is Point two-section calcining calcines 1-2h including being warming up to 250-300 DEG C of heat preservation with the heating rate of 0.5-2 DEG C/min, then with 2-10 DEG C/ The heating rate of min is warming up to 600-800 DEG C of heat preservation calcining 1-4h.

7. flexibility magnalium composite oxides nano fibrous membrane according to claim 1, it is characterised in that: the colloidal sol- Gel method combination electrostatic spinning technique, which refers to, is placed in each group in solvent, after stirring hydrolysis, then obtains doing by electrostatic spinning and coagulate Glue.

8. flexibility magnalium composite oxides nano fibrous membrane according to claim 7, it is characterised in that: the hydrolysis when Between be 6-12h.

9. a kind of preparation method of flexible magnalium composite oxides nano fibrous membrane according to claim 1-8, Characterized by the following steps:

(1) silicon source, magnesium source, dopant, spin finish aid are added in solvent, sour regulation system pH is 2-3, water after stirring and dissolving Solution, obtains colloidal sol spinning solution；

(2) colloidal sol spinning solution is subjected to electrostatic spinning, obtains presoma xerogel tunica fibrosa；

(3) presoma xerogel tunica fibrosa is subjected to calcine by steps, obtains flexible magnalium composite oxides nano fibrous membrane.

10. the described in any item flexible magnalium composite oxides nano fibrous membranes of claim 1-8 repair field in environmental improvement In application.

Technical field

The invention belongs to inorganic nano-fiber field of material technology, in particular to a kind of flexible magnalium composite oxides nanometer Tunica fibrosa and preparation method thereof and the application in environmental improvement reparation field, especially suitable for heavy metal adsorption field.

Background technique

With the fast development of the industry such as China's mining, chemical industry, pesticide, dyestuff, metallurgy and battery, largely contain heavy metal Waste be directly or indirectly discharged into environment, since heavy metal cannot be biodegradable and easily be assembled, food chain can be passed through Into human body, health and ecosystem balance to the mankind cause serious threat, thus to the prevention and control of heavy metal pollution and Improvement has become environmental problem very in the urgent need to address in various countries' environmental protection.Currently, in order to which heavy metal is effectively reduced Injury to environment and the mankind, many technology and methods have been used for repairing heavy metal pollution, such as the precipitation method, chemical oxidation/go back Former, film filtering, ion exchange and absorption method etc..Wherein, absorption method has the characteristics that high-efficient, flexibility is good, easy to operate, fits For water body and heavy metal in soil reparation, therefore exploitation preparation process is simple, high property low in cost and being not easy secondary pollution Energy adsorbent is of great significance to the improvement of heavy metal.

Magnalium metal composite oxide nano material is a kind of common adsorbent, mutually friendly, cheap with environment, The features such as adsorption capacity is high, physical and chemical stability is high, it is applied widely, it can be suitably used for Pb²⁺、Cd²⁺、Cu²⁺、Hg²⁺Equal cations Type heavy metal ion, CrO₄ ^2-、AsO₄ ^3-The removal of equal anionics pollutant and organic pollutant.Li(Environmental Science:Nano, 2016,3 (1): 94-106.) etc. have studied mesoporous magnalium composite oxides to the absorption property of arsenic, have High AsO₂ ^-And AsO₄ ^3-Scavenging activity, and with the increase of content of magnesium, absorption property significantly improves.However, usual metal Oxide is macroscopically mostly dusty material, and surface position can be higher, is easy itself and reunites, and there are one to environment for nano material Fixed ecotoxicity effect will cause secondary pollution, therefore greatly limit its extensive use as adsorbent.

Electrostatic spinning technique is a kind of process that lower polymer solution progress spinning is acted on using high-pressure electrostatic, can be used for making Standby organic polymer fiber, natural polymer nanofiber, Organic-inorganic composite nanofiber and inorganic nano-fiber, institute The nano fibrous membrane obtained has many advantages, such as that large specific surface area, porosity are high, size is easy to control, the easy functionalization in surface, in biology The fields such as medicine, environmental project and weaving have very high application value (Progress in Polymer Science, 2018,77:69-94.).Patent CN102758310A and CN102167567A disclose a kind of flexibility γ-Al respectively₂O₃Nanowire Peacekeeping flexibility α-Al₂O₃Nanofiber, resulting fiber is uniformly and continuous, and not easy to break and mechanical property is excellent, has preferable Flexibility and thermal stability are good.Patent CN107159152A discloses a kind of preparation of membranaceous alumina base catalyst of flexible fiber Method, and have studied its catalytic degradation performance to organic contamination in water.

Currently, flexible alumina nano fiber film is mainly used for high temperature insulating material or catalyst carrier.Magnesia and oxygen Changing aluminium is excellent heavy metal absorbent, however prepares flexible magnalium composite oxides nanofiber based on electrostatic spinning technique There is not been reported for film, and major limitation is metal oxide with the increase of calcination temperature and time, the size of crystallographic grain Constantly increase, and mutually assemble, be coupled, destroys the integrality of fibre structure, lead to being remarkably decreased for fibre strength, and its conduct A kind of adsorbent is used for environment remediation, has applied widely, highly-safe, the without secondary pollution and spies such as recycling convenient separation Point provides a kind of new strategy for environment remediation.

Summary of the invention

In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of flexible magnalium Composite oxides nano fibrous membrane.

Flexibility magnalium composite oxides nano fibrous membrane of the invention is prepared by using electrostatic spinning technique, has excellent Different mechanical strength and flexibility is convenient for recycling and reusing, opens new approach to expand the utilization of magnalium composite oxides.

Another object of the present invention is to provide a kind of preparation method of above-mentioned flexible magnalium composite oxides nano fibrous membrane.

Still a further object of the present invention is to provide above-mentioned flexible magnalium composite oxides nano fibrous membrane in environmental improvement reparation Application in application in field, especially heavy metal adsorption field.

The purpose of the present invention is realized by following proposal:

A kind of flexibility magnalium composite oxides nano fibrous membrane, using silicon source, magnesium source as raw material, yttrium salt is dopant, and acid is At least one of hydrolyst, polyvinylpyrrolidone and polyethylene glycol oxide passes through in dicyandiamide solution as spin finish aid Sol-gel method combination electrostatic spinning technique obtains xerogel fiber, then segmented calcining is made.

The molar ratio of the magnesium source and silicon source is preferably 1:9-3:7.

The molar ratio of the dopant and silicon source is preferably 1:10-1:50.

The silicon source is water-soluble aluminum salt, such as aluminium chloride, aluminium isopropoxide, aluminum nitrate, preferably aluminium isopropoxide and chlorine Change at least one of aluminium, aluminum nitrate etc.；More preferably molar ratio be 1:3-1:5 aluminium chloride and aluminium isopropoxide.

The magnesium source is at least one of water-soluble magnesium salt, such as magnesium nitrate, magnesium chloride, magnesium acetate.

The yttrium salt may include yttrium nitrate, yttrium chloride etc..

The acid can be acetic acid, hydrochloric acid or nitric acid.

The additional amount of source of aluminium is preferably the 10-30% of system gross mass.

The dosage of the spin finish aid is conventional amount used, the preferably 2-5% of system gross mass.

The weight average molecular weight that the polyethylene adjoins pyrrolidone (PVP) is preferably 36-130w, more preferably 130w.

The weight average molecular weight of the polyethylene glycol oxide (PEO) is preferably 60-100w, more preferably 100w.

The solvent is preferably ethanol water, more preferably volume ratio be 2:1-1:2 ethanol/water.

The sol-gel method combination electrostatic spinning technique, which refers to, is placed in each group in solvent, after stirring hydrolysis, then leads to It crosses electrostatic spinning and obtains xerogel.

Further, the time of the hydrolysis is preferably 6-12h；It is preferred that carrying out at room temperature.

Further, the process conditions of the electrostatic spinning are preferred are as follows: voltage 15-25KV；Spinning solution sprays rate: 0.5-1.2mL/h；Receive distance: 12-20cm；Environment temperature: 20-30 DEG C；Ambient humidity: 40-50%.It receives distance and refers to spinning Distance of the syringe needle to reception device.

The calcining preferably divides two-section calcining, is included in 250-300 DEG C of calcining 1-2h, then be warming up to 600-800 DEG C Calcine 1-4h；250-300 DEG C of heat preservation calcining 1-2h is more preferably warming up to the heating rate of 0.5-2 DEG C/min, then with 2-10 DEG C/heating rate of min is warming up to 600-800 DEG C of heat preservation calcining 1-4h.

The pH of the dicyandiamide solution is preferably 2-3, can be adjusted and be realized by acetic acid, hydrochloric acid or nitric acid.In the method for the present invention The inorganic acids such as acetic acid, hydrochloric acid or nitric acid be both used as hydrolyst, also have both the effect of regulation system pH.

The present invention also provides a kind of preparation methods of above-mentioned flexible magnalium composite oxides nano fibrous membrane, including following step It is rapid:

(1) silicon source, magnesium source, dopant, spin finish aid are added in solvent, sour regulation system pH is 2-3, after stirring and dissolving Hydrolysis, obtains colloidal sol spinning solution；

(2) colloidal sol spinning solution is subjected to electrostatic spinning, obtains presoma xerogel tunica fibrosa；

(3) presoma xerogel tunica fibrosa is subjected to calcine by steps, obtains flexible magnalium composite oxides nano fibrous membrane.

In step (1), preferably first silicon source, magnesium source, dopant are added in solvent, sour regulation system pH is 2-3, is added Spin finish aid.The spin finish aid is preferred before being added to be stirred to system solution clarification.

In step (3), the calcining is preferably carried out in Muffle furnace or tube furnace.

The present invention prepares flexible magnalium composite oxides nanofiber by sol-gel method combination electrostatic spinning technique, It is simple with preparation process, easy to operate, it is convenient for scale industrial production and application.Magnalium oxide is a kind of common absorption Agent has the features such as environment is mutually friendly, cheap, and adsorption capacity is high, physical and chemical stability is high, applied widely.But by In metal oxide as the increase of calcination temperature and time, the partial size of crystal grain constantly increase and assemble, excessive fibre is generated Defect in tieing up, leads to the concentration of fiber internal stress, fibre strength is remarkably decreased, thus flexible material can not be prepared.This Invention, as dopant, effectively inhibits the growth of metal oxide crystal grain, to obtain smaller crystalline substance by addition rare earth element y Grain partial size, and using amorphous oxide as substrate, deformation is generated under outer stress, it can effectively dispersive stress and generation Biggish deformation, in conjunction with the flexible magnalium composite oxides nano fibrous membrane that electrostatic spinning is prepared, have bigger serface, High porosity, and excellent in mechanical performance, flexibility are good, have adsorption rate rate fast as adsorbent material, the spies such as removal rate height Point reaches 135.34mg/g to the adsorption capacity of heavy metal chromium；And macroscopically flexible membranous structure is effectively prevented from powdered gold Belong to oxide to be easy to reunite as adsorbent, be difficult to the disadvantages of recycling, thus it has very well in environmental improvement reparation field Cost advantage and wide application prospect, especially can be widely applied to dirty for remediating heavy metal in heavy metal adsorption field Dye.

The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that

(1) present invention provides a kind of flexible magnalium composite oxides nano fibrous membrane, flexibility with higher and machine Tool intensity, even in fiber diameter distribution and controllable.

(2) flexible magnalium composite oxides nano fibrous membrane of the invention, which is applied to environment remediation, has widely applicable model It encloses and applicable object.

(3) there is physics simultaneously in the adsorbent material adsorption process of the flexible magnalium composite oxides nano fibrous membrane of the present invention Absorption and chemisorption, fast to the removal rate of heavy metal, removal rate effect is high.

(4) preparation method simple process of the invention, operate conveniently, convenient for scale and industrialized production and application.

Detailed description of the invention

Fig. 1 is the infrared spectrogram of the flexible magnalium composite oxides nano fibrous membrane of embodiment 1.

Fig. 2 is the presoma xerogel nano fibrous membrane thermogravimetric curve of embodiment 1.

Fig. 3 is the SEM figure of the flexible magnalium composite oxides nano fibrous membrane of embodiment 1.

Fig. 4 is optical photograph and the nano fibrous membrane bending of the flexible magnalium composite oxides nano fibrous membrane of embodiment 1 Optical photograph afterwards.

Fig. 5 is the surface Zeta potential distribution map of the flexible magnalium composite oxides nano fibrous membrane of embodiment 1.

Specific embodiment

Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.

Material involved in the following example can be obtained from commercial channel.Dosage of each component in terms of quality parts by volume, g, mL.Electrostatic spinning apparatus used in embodiment be Beijing Yongkang work in peace and contentment development in science and technology Co., Ltd production E-2 type Static Spinning Silk machine.

Wherein, adsorption step is as follows: magnalium composite oxides nano fibrous membrane is added in heavy metal Cr (VI) solution, Concentration is 10-400mg/L, and adsorbent dosage is 5-200mg, pH value 3, time of contact 0.5-10h, temperature 298K, With the speed oscillation of 150rpm, then it is separated by filtration.