CN114588884B - Preparation method and application of polyimide dioxime/polyethyleneimine composite film - Google Patents
Preparation method and application of polyimide dioxime/polyethyleneimine composite film Download PDFInfo
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- CN114588884B CN114588884B CN202210202754.XA CN202210202754A CN114588884B CN 114588884 B CN114588884 B CN 114588884B CN 202210202754 A CN202210202754 A CN 202210202754A CN 114588884 B CN114588884 B CN 114588884B
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- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- Y02P10/20—Recycling
Abstract
The invention discloses a preparation method and application of a polyimide dioxime/polyethyleneimine composite film. The method comprises the following steps: preparing a polyimide dioxime solution; mixing a polyimide dioxime solution with a polyethyleneimine solution at room temperature to obtain a polyimide dioxime/polyethyleneimine composite solution; and uniformly coating the composite solution on a glass slide and heating to obtain the polyimide dioxime/polyethyleneimine composite film. The polyimide dioxime/polyethyleneimine composite membrane prepared by the method is applied to adsorbing Pt (IV) in a waste noble metal catalyst. The invention uses industrial polyacrylonitrile with low cost and no pollution, utilizes the crosslinking effect of polyethyleneimine, provides a simple and rapid method capable of producing the polymeric film on a large scale, is beneficial to industrial production and preparation, and provides a good prospect for the application of the adsorbent material in the industrial direction in the subsequent experiments.
Description
Technical Field
The invention relates to the field of adsorption recovery of noble metal Pt (IV) in a waste noble metal catalyst, in particular to a preparation method and application of a polyimide dioxime/polyethyleneimine composite membrane.
Background
With the rapid development of world economy, platinum group elements, particularly platinum, are widely used in the fields of catalysts, fuel cells, jewelry, automobiles, electronics, medical devices, and the like, because of their excellent physicochemical properties as one of noble metals. The extraction of platinum from ores is not satisfactory, and furthermore, the platinum metal in the waste such as noble metal catalysts, electronic equipment and the like is harmful to the environment if not treated. Therefore, the method for recycling the noble metal platinum from the pollutants such as electronic waste, waste catalyst and the like is significant. The main recovery method is (1) hydrometallurgy, wherein the noble metals in the ores and the catalytic waste are dissolved by aqua regia, and the ores and the catalytic waste are recovered by an adsorbent. (2) Flocculation/fire method, extracting the enriched noble metal by the traditional precipitation extraction technology, has the defects of insufficient recovery, low selectivity and the like. (3) Biological metallurgy has high selectivity and strong environmental adaptability, but mechanism research is still in the initial stage, and is difficult to adapt to industrialization. Therefore, compared with other recovery methods, adsorption has great advantages, and innovative adsorption processes have been studied, wherein the key influencing the adsorption performance of platinum group elements depends on the specific functional groups of the adsorbent, the abundant active sites and the excellent morphology structure.
Compared with the traditional physical adsorbent such as zeolite which relies on pore canal for simple collection adsorption, the adsorbent which can chemically react with and form bonds with platinum group elements has higher attraction. For example, porphyrin adsorbent COP-180 containing rich amine groups realizes efficient adsorption of platinum, and porous polymer POP-oNH containing rich amine groups 2 Py to enable rapid combined extraction of palladium; therefore, efficient selective binding of platinum group elements requires the design of a material rich in functional groups such as amine groups and the like. In addition to specific chemical binding, the microstructure of the adsorbent is critical to the adsorption rate and active site distribution, e.g., an amine-containing composite membrane PU/UiO-66-NH with porous MOF structure 2 So as to realize the selective adsorption of platinum group elements and the rapid adsorption of noble metals by the CNT/PAH film with a porous framework. However, the adsorbents having the porous structure all require the introduction of functional groups from the outside, and have a problem of a certain binding efficiency.
Polyacrylonitrile is often used as a polymeric film substrate by excellent electrospinning characteristics. Polyamide oxime and polyimide dioxime with rich functional groups are obtained after oximation reaction of polyacrylonitrile and are widely used for extracting nuclide uranium from sea water, such as polyimide dioxime/sodium alginate sponge, polyamidoxime hydrogel film and the like, and although the polyimide dioxime has rich functional groups, the polyimide dioxime is subjected to processing modification polymerization for normal use, so that the density and compactness of the adsorbent are certainly increased, mass transfer is slow, and the adsorption rate is influenced. Meanwhile, the preparation process and flow are complicated, the electrostatic spinning and irradiation grafting equipment is expensive, the operation is complex, and the large-scale production is not facilitated. Therefore, how to effectively utilize the abundant functional groups of polyimide dioxime and prepare a composite film through simple experimental conditions has been the subject of research.
Here, we propose a simple and rapid method for preparing porous polyimide dioxime/polyethyleneimine porous membrane on a large scale, and use the prepared porous membrane for extraction and recovery of noble metal platinum. By simply introducing polyethyleneimine, the rich amine groups of polyethyleneimine are utilized to crosslink with polyimide dioxime, so that more functional groups are provided, more pore diameters are brought by crosslinking, and a forming effect is provided, and the polyethyleneimine is used as a common membrane substrate. And obtaining the composite film after simple coating pyrolysis. The porous material has excellent flexibility and strength, can be prepared in a template mode on a large scale, is beneficial to being used in various environments, and simultaneously has a cross-linked hierarchical pore structure and richer functional groups, so that the adsorption rate and the adsorption efficiency are effectively improved. The method has excellent adsorption recovery performance on noble metal platinum in the actual waste noble metal catalyst, and provides a new idea for industrial recovery application of the waste noble metal catalyst.
Disclosure of Invention
Aiming at the problems and the proposed feasible method, the invention provides a preparation method and application of a polyimide dioxime/polyethyleneimine composite membrane. The method not only solves the defects of low selectivity and adsorption performance of the traditional adsorbent on noble metal, but also can be rapidly prepared by a simple coating pyrolysis method, has simple preparation and convenient operation, and particularly can realize template regulation and mass production, and further achieves the aim of high-efficiency, rapid and repeated cycle removal of noble metal Pt (IV).
A preparation method of polyimide dioxime/polyethylenimine composite film, first prepare polyimide dioxime solution; mixing and stirring a polyimide dioxime solution and a polyethyleneimine solution to obtain a polyimide dioxime/polyethyleneimine composite solution; and uniformly coating the polyimide dioxime/polyethyleneimine composite solution on a glass slide, and heating to obtain the polyimide dioxime/polyethyleneimine composite film.
The invention is realized by the following technical scheme:
a preparation method of a polyimide dioxime/polyethyleneimine composite film comprises the following steps:
(1) Preparing a polyimide dioxime solution;
(2) Mixing and stirring a polyimide dioxime solution and a polyethyleneimine solution to obtain a polyimide dioxime/polyethyleneimine composite solution;
(3) And uniformly coating the composite solution on a substrate and heating to obtain the polyimide dioxime/polyethyleneimine composite film.
Further, the step (1) includes: adding hydroxylamine hydrochloride, sodium hydroxide and polyacrylonitrile into N, N-dimethylformamide, stirring for 1-3 h, heating, continuously stirring for 10-14 h, and finally centrifuging to obtain the polyimide dioxime solution.
In step (1), hydroxylamine hydrochloride: sodium hydroxide: polyacrylonitrile: the ratio of the N, N-dimethylformamide solution is 10-18 g: 8-12 g: 8-12 g: 80-100 mL. For example, hydroxylamine hydrochloride: sodium hydroxide: polyacrylonitrile: the ratio of the N, N-dimethylformamide solution is 10-18 g: 8-12 g: 8-12 g: 80-100 mL or 11-18 g: 9-12 g: 9-12 g: 80-100 mL or 12-18 g: 10-12 g: 10-12 g: 80-100 mL or 13-18 g: 11-12 g: 11-12 g: 80-100 mL or 14-18 g:12g:12g: 80-100 mL.
Further, in step (1), hydroxylamine hydrochloride: sodium hydroxide: polyacrylonitrile: the ratio of N, N-dimethylformamide solution was 14g:10g:10g:100mL.
Further, in the step (1), the heating temperature is 70 to 100 ℃, for example, the heating temperature is 70, 75, 80, 85, 90, 95 or 100 ℃. The stirring speed is 900-1100 rpm, and the stirring time is 10-14 h.
In the step (1), more than one centrifugation operation is performed in the centrifugation step, the centrifugation rotating speed is 8000-10000 rpm, and the time is 3-8 min.
In the step (2), the mass ratio of polyimide dioxime to polyethyleneimine is 1:3-3:1. Preferably, the mass ratio of polyimide dioxime to polyethyleneimine is 1:1.
Further, in the step (2), 100mL of the prepared polyimide-dioxime solution and 100mL of the polyethyleneimine solution are mixed, and stirred at room temperature, wherein the stirring speed is 900-1100 rpm, and the time is 30-60 min.
Further, in the step (3), the size of the rectangular glass slide is 1cm multiplied by 3cm, the pyrolysis temperature is 40-60 ℃, and the time is 5-10 min.
In the step (3), the heating temperature is 40-60 ℃ and the time is 5-10 min. For example, the heating temperature is 40, 45, 505, 55 or 60 ℃.
The invention provides an application of a polyimide dioxime/polyethyleneimine composite film prepared by the method in any one of the above to the adsorption of noble metal Pt (IV).
Further, the dosage of the polyimide dioxime/polyethyleneimine composite film in the water body is 0.01-0.03 g/L.
Further, the adsorbent is adsorbed in Pt (IV) water solution for 23-25 h, and the pH of the water body is 1.0-3.0.
Specifically, the preparation method of the polyimide dioxime/polyethyleneimine composite film comprises the following steps:
(1) 14g of hydroxylamine hydrochloride, 10g of sodium hydroxide and 10g of polyacrylonitrile are added into 100mL of N, N-dimethylformamide solution and stirred vigorously for 2 hours, then heated and stirred continuously for 12 hours, and finally centrifuged to obtain polyimide dioxime solution.
(2) Mixing and stirring 100mL of polyimide dioxime solution and 100mL of polyethyleneimine solution for 40min to obtain polyimide dioxime/polyethyleneimine composite solution;
(3) Uniformly coating the polyimide dioxime/polyethyleneimine composite solution on a glass slide, and heating at 50 ℃ for 8min to obtain the polyimide dioxime/polyethyleneimine composite film.
Specifically, in the step (1), the hydroxylamine hydrochloride, sodium hydroxide and polyacrylonitrile are added while stirring.
Specifically, in the above step (1), the stirring speed was 1000rpm.
Specifically, in the step (1), the centrifugal speed was 9000rpm and the time was 4min.
Specifically, in the step (2), the proportion of the 100mL polyethyleneimine solution is polyethyleneimine: the N, N-dimethylformamide solution was 2mL:98mL.
Specifically, in the step (3), the slide glass is rectangular. The rectangular slide was 1cm by 3cm in size.
Specifically, in the step (2), the reaction temperatures are all room temperature.
The invention also provides application of the polyimide dioxime/polyethyleneimine composite membrane in adsorbing noble metal Pt (IV), wherein the dosage of the polyimide dioxime/polyethyleneimine composite membrane in a water body is 0.02g/L, the adsorption treatment time is 24 hours, and the pH value of the adsorbed water body is adjusted to be 2.
According to the technical scheme, the beneficial effects of the invention are as follows:
(1) The polyimide dioxime/polyethyleneimine composite membrane provided by the invention is a settable polyimide dioxime/polyethyleneimine composite membrane with a hierarchical porous structure, which is obtained by self-crosslinking and crosslinking polymerization of a polyimide dioxime long chain and polyethyleneimine under a heating synthesis strategy which is simple in process, quick in preparation and easy for template batch production. Because of the unique three-dimensional layered hierarchical pore structure, rich functional groups, higher surface area and a large number of active sites, the composite membrane can be used as an adsorbent for Pt (IV) in a waste noble metal catalyst, achieves the purposes of efficient, rapid and selective adsorption and recovery of rare metal resources Pt (IV) in waste, has flexible environmental adaptability, can be used in a wider pH range, can circularly remove Pt (IV) in the waste noble metal catalyst, has a reduction effect on platinum, and has excellent noble metal recovery and development characteristics.
(2) The saturated adsorption capacity of the polyimide dioxime/polyethyleneimine composite membrane prepared by the invention to Pt (IV) can reach 4185mg/g;0.02g/L of adsorbent was able to achieve 99% removal of 1ppm Pt (IV) in 8min, with a substantial equilibrium reached in 12 min; and Pt (IV) can be adsorbed and reduced.
Drawings
In order to more accurately and properly explain the technical solutions of the embodiments of the present invention, the drawings needed in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope and a physical image photograph of a polyimide dioxime/polyethyleneimine composite film prepared in this example;
FIG. 2 is a Fourier transform infrared spectrum of a polyimide dioxime/polyethyleneimine composite film prepared in this example;
FIG. 3 is a schematic diagram showing the adsorption effect of the polyimide dioxime/polyethyleneimine composite film prepared in this example on noble metal Pt (IV) and the fitting result;
FIG. 4 is a graph showing adsorption kinetics of the polyimide dioxime/polyethyleneimine composite film prepared in this example to noble metal Pt (IV) at different time points and fitting results;
FIG. 5 is an X-ray diffraction pattern of the polyimide dioxime/polyethyleneimine composite film prepared in this example after adsorption of noble metal Pt (IV).
Detailed Description
The following description of the embodiments of the present invention will be made clearly and perfectly with reference to the accompanying drawings of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The preparation method and application of the polyimide dioxime/polyethyleneimine composite film provided by the invention are described in detail below. What is not described in detail in the embodiments of the present invention belongs to the prior art known to those skilled in the art.
Example 1
A preparation method of polyimide dioxime/polyethylenimine composite film, first prepare polyimide dioxime solution; preparing a polyimide dioxime solution; mixing and stirring a polyimide dioxime solution and a polyethyleneimine solution to obtain a polyimide dioxime/polyethyleneimine composite solution; uniformly coating the polyimide dioxime/polyethyleneimine composite solution on a glass slide and heating to obtain the polyimide dioxime/polyethyleneimine composite film, wherein the specific preparation method comprises the following steps of:
(1) 14g of hydroxylamine hydrochloride, 10g of sodium hydroxide and 10g of polyacrylonitrile (M.w.150000) were added to 100ml of N, N-dimethylformamide solution and stirred vigorously for 2 hours. Stirring is then continued for 12h at 80℃with a stirring speed of 1000rpm, and finally centrifugation is carried out for 5min at 8000rpm, ensuring complete oximation of the polyacrylonitrile and obtaining 10g/mL of polyimide dioxime supernatant.
(2) At room temperature, a 10g/L solution of polyethylenimine (M.w.70000) was first prepared with deionized water. Mixing and stirring 100mL of the polyimide dioxime supernatant with 100mL of the polyethyleneimine solution for 40min to obtain a polyimide dioxime/polyethyleneimine composite solution, wherein the stirring speed is 1000rpm;
(3) The polyimide dioxime/polyethyleneimine composite solution was uniformly coated on a rectangular slide glass (slide glass size: 1 cm. Times.3 cm) and heated at 50℃for 8 minutes, to obtain a polyimide dioxime/polyethyleneimine composite film (thickness: 85 μm).
Further, the polyimide dioxime/polyethyleneimine composite film prepared according to the above-described preparation method.
Furthermore, the embodiment also provides a polyimide dioxime/polyethyleneimine composite membrane which is directly used as an adsorbent for adsorbing Pt (IV) in noble metal, wherein the dosage of the adsorbent in a water body is 0.02g/L, and the pH value of the water body is controlled to be 2 and the time of adsorption treatment is controlled to be 24 hours before the adsorbent is subjected to adsorption treatment. In practical application, the adsorption performance of the adsorbent provided by the invention on the noble metal Pt (IV) of the water body can be tested by adopting the following scheme: firstly, preparing Pt (IV) solution with a certain concentration, regulating the temperature and the pH value of the solution, adding the adsorbent provided by the invention, continuously stirring, and measuring the content of Pt (IV) by ICP (inductively coupled plasma), thereby obtaining the adsorption capacity of the adsorbent to Pt (IV); preparing 1ppm Pt (IV) solution, adding the adsorbent provided by the invention when the optimal pH value and temperature of the mixed solution are reached, sampling a certain amount of liquid every time a period of time, and measuring the content of Pt (IV) by ICP (inductively coupled plasma), namely the adsorption effect of the polyimide dioxime/polyethyleneimine composite membrane on Pt (IV) at different adsorption times.
Analysis of results:
the polyimide dioxime/polyethyleneimine composite film prepared by the embodiment of the invention is subjected to microstructure observation, component analysis and performance detection, so that the following experimental results are obtained:
(1) The polyimide dioxime/polyethyleneimine composite film prepared by the embodiment of the invention is subjected to macroscopic shooting and microstructure observation by adopting a camera and a scanning electron microscope (SU 8020, hitachi), so that a picture shown in the figure 1 is obtained; wherein, figure 1 is a picture of a polyimide dioxime/polyethyleneimine composite membrane scanning electron microscope prepared in the embodiment of the invention, and clearly shows a microscopically abundant porous structure and a three-dimensional hierarchical porous structure with different pore diameters under high power, which shows that the porous structure has a hierarchical porous structure. Fig. 1 is an illustration showing a physical photograph of the polyimide dioxime/polyethyleneimine composite film prepared in this example, showing the mass preparation and the transparent light and thin properties of the polyimide dioxime/polyethyleneimine composite film.
(2) The polyimide dioxime/polyethyleneimine composite film prepared in the embodiment of the invention is subjected to component analysis by using a fourier transform infrared spectrometer (NEXUS, thermo Nicolet), so that a fourier transform infrared spectrum shown in fig. 2 is obtained. As can be seen from fig. 2: polyimide dioxime characteristic peaks (1638 cm) appear in the polyimide dioxime/polyethyleneimine composite film -1 、1470cm -1 And 943cm -1 ) Peak characteristic of polyethylene diamine (1576 cm) -1 、1311cm -1 、1117cm -1 And 817cm -1 ). The position of the infrared peak of the final prepared product of the embodiment of the invention can correspond to the characteristic peak of polyimide dioxime/polyethyleneimine functional groups. Watch (watch)Successful synthesis of polyimide dioxime/polyethyleneimine composite membrane was demonstrated.
(3) The adsorption isotherm test for Pt (IV) was performed using the polyimide dioxime/polyethyleneimine composite film prepared in example 1 of the present invention as an adsorbent. Specifically: preparing Pt (IV) solutions of 1ppm, 10ppm, 20ppm, 50ppm, 100ppm, 200ppm and 500ppm respectively in 30mL and adjusting the pH to 2, then adding 0.6mg of the polyimide-dioxime/polyethyleneimine composite membrane provided by the embodiment of the invention into each solution as an adsorbent, continuously stirring at 25 ℃ for 24 hours, removing part of the liquid by using a 0.22 mu m filter membrane, collecting filtrate, marking, and respectively detecting the concentration of the Pt (IV), thereby obtaining a schematic diagram of the adsorption effect of the Pt (IV) in water under different Pt (IV) concentration conditions as shown in figure 3. As can be seen from fig. 3: the polyimide dioxime/polyethyleneimine composite film provided by the embodiment 1 of the invention has the adsorption capacity which is continuously increased along with the increase of the concentration of Pt (IV) when the concentration of Pt (IV) is lower; and after the initial Pt (IV) concentration exceeds 200ppm, the adsorption quantity changes little along with the increase of Pt (IV), and finally, the balance is achieved; langmuir fitting results demonstrate: the process of adsorbing Pt (IV) belongs to monolayer chemisorption; according to the Langmuir adsorption model calculation, the maximum removal amount of Pt (IV) in the water body of the polyimide dioxime/polyethyleneimine composite membrane provided by the embodiment 1 of the invention can reach 4185mg/g, which is far more than that of the currently reported adsorbent.
(4) The polyimide dioxime/polyethyleneimine composite film prepared by the embodiment of the invention is used as an adsorbent to carry out an adsorption kinetics test on Pt (IV), and the content of Pt (IV) is measured by ICP, so that the removal rate of the adsorbent on Pt (IV) is obtained. Specifically: preparing 1L of Pt (IV) adsorption test solution with the concentration of 1 ppm; the pH value of the adsorption test liquid is regulated to 2 by 0.01M hydrochloric acid or potassium hydroxide; then, 1g of the polyimide dioxime/polyethyleneimine composite membrane prepared in the embodiment 1 of the invention is respectively added into Pt (IV) adsorption test liquid and is timed; continuously stirring at 25 ℃, respectively removing part of liquid from the solution at the time points of 30s, 1min, 2min, 4min, 8min, 10min, 12min, 15min, 20min, 25min, 30min and 40min by using a filter membrane with the thickness of 0.22 mu m, collecting filtrate, marking, and finally measuring the concentration of Pt (IV) in the filtrate at different time points by using ICP, thereby obtaining an adsorption effect schematic diagram of the different adsorption time on the Pt (IV) as shown in figure 4; wherein, fig. 4 (a) is an adsorption kinetic graph of Pt (IV) by the polyimide dioxime/polyethyleneimine composite film prepared in example 1 of the present invention; fig. 4 (b) is a schematic representation after fitting using a quasi-secondary adsorption kinetic model. As can be seen from fig. 4: the polyimide dioxime/polyethyleneimine composite film prepared in the embodiment 1 of the invention has good Pt (IV) adsorption effect and higher removal performance, and the polyimide dioxime/polyethyleneimine composite film prepared in the embodiment 1 of the invention can reach adsorption equilibrium within 12min and has higher adsorption efficiency.
(5) The polyimide dioxime/polyethyleneimine composite film prepared in the embodiment of the invention was subjected to component analysis by using an X-ray diffractometer (X' pert Pro, philips), thereby obtaining an X-ray diffraction pattern as shown in fig. 5. As can be seen from fig. 5: characteristic peaks of platinum atoms (39.8 °, 46.9 °, 67.8 °, 81.8 ° and 85.6 °) appear in the polyimide dioxime/polyethyleneimine composite film. Indicating that the finally prepared adsorbent of the example of the invention has a reducing effect in the adsorption process of platinum.
In summary, the embodiment of the invention develops a strategy for preparing the novel polyimide dioxime/polyethyleneimine composite membrane with the three-dimensional layered hierarchical pore structure on a large scale by using a template with simple operation and rapid synthesis, and the composite membrane can efficiently, spontaneously and rapidly recover noble metal platinum at room temperature. Because of the excellent pore canal structure, higher binding site and rich functional groups, the catalyst has ultrahigh adsorption performance on noble metal platinum, and simultaneously has low production cost, easy mass production and the like, and Pt (IV) in the waste noble metal catalyst can be efficiently, quickly and adsorbed and reduced for recycling.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the polyimide dioxime/polyethyleneimine composite film is characterized by comprising the following steps of:
(1) Preparing a polyimide dioxime solution;
(2) Mixing and stirring a polyimide dioxime solution and a polyethyleneimine solution to obtain a polyimide dioxime/polyethyleneimine composite solution;
(3) Uniformly coating the composite solution on a substrate and heating to obtain a polyimide dioxime/polyethyleneimine composite film;
the step (1) comprises: adding hydroxylamine hydrochloride, sodium hydroxide and polyacrylonitrile into N, N-dimethylformamide, stirring for 1-3 h, heating, continuously stirring for 10-14 h, and finally centrifuging to obtain the polyimide dioxime solution.
2. The method of claim 1, wherein in step (1), hydroxylamine hydrochloride: sodium hydroxide: polyacrylonitrile: the ratio of the N, N-dimethylformamide solution is 10-18 g: 8-12 g: 8-12 g: 80-100 mL.
3. The method of claim 1, wherein in step (1), hydroxylamine hydrochloride: sodium hydroxide: polyacrylonitrile: the ratio of the N, N-dimethylformamide solution was 14g:10g:10g:100 And (3) mL.
4. The method of claim 1, wherein in step (1), the heating temperature is 70-100 ℃.
5. The method of claim 1, wherein in the step (1), the centrifugal speed is 8000-10000 rpm, and the time is 3-8 min.
6. The method of claim 1, wherein in the step (2), the mass ratio of polyimide dioxime to polyethyleneimine is 1:3 to 3:1.
7. The method according to claim 1, wherein in the step (3), the heating temperature is 40-60 ℃ for 5-10 min.
8. Use of the polyimide dioxime/polyethyleneimine composite film prepared by the method of any one of claims 1 to 7 for the adsorption of noble metals Pt (IV).
9. The application of claim 8, wherein the polyimide-dioxime/polyethyleneimine composite film is used in water in an amount of 0.01-0.03 g/L.
10. The use according to claim 8, wherein the adsorbent is adsorbed in an aqueous Pt (IV) solution for a period of time of 23-25 hours and the pH of the water is 1.0-3.0.
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| CN109734832B (en) * | 2019-01-09 | 2021-08-03 | 海南大学 | Water-soluble amidoxime group polymer and preparation method and application thereof |
| CN112452299B (en) * | 2020-12-09 | 2022-04-05 | 山东大学 | MXene-based three-dimensional porous flexible self-supporting film, preparation method thereof and application thereof in electrochemical adsorption of dye |
| CN113035470B (en) * | 2021-03-16 | 2022-03-15 | 东华大学 | Polyimide composite membrane and preparation method and application thereof |
| CN113231043B (en) * | 2021-05-06 | 2022-08-02 | 哈尔滨工程大学 | Oximato multi-layer polyimide microsphere adsorption material and preparation method thereof |
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