CN107935018B - Preparation method of two-dimensional transition metal nano-sheet with structure memory - Google Patents
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Abstract
The invention belongs to the field of material science and environmental engineering, and discloses a preparation method of a two-dimensional transition metal nano sheet with structure memory. The method comprises the steps of taking a calcination product LDO of the magnesium-aluminum layered double hydroxide prepared by a coprecipitation method as a precursor, adsorbing copper ions in water, and calcining to form the two-dimensional nano sheet material with the structure memory effect and uniformly dispersed copper oxide. The structure memory two-dimensional transition metal nano-sheet material prepared by the invention is used for activating persulfate and efficiently degrading phenolic organic pollutants in a multi-phase system, has low leaching amount of harmful metals, low cost and environmental protection, provides a simple, convenient and efficient method for treating the phenolic pollutants, has good economic and environmental benefits, and can be produced and applied in a large scale.
Description
Technical Field
The invention belongs to the field of material science and environmental engineering, and particularly relates to a preparation method of a two-dimensional transition metal nano sheet with structure memory.
Background
The phenol pollutant is one of important pollutants in industrial production, and becomes a priority control toxic pollutant due to stable structure, difficult degradation and high toxicity. Over the years, many researchers degrade phenolic pollutants by adopting methods such as biodegradation, activated carbon adsorption and air catalytic oxidation, but most of the methods are only suitable for treatment with small discharge capacity and low concentration, and have the defects of long treatment time, narrow application range, high cost, incomplete degradation, easy secondary pollution and the like, so that the development of the methods is limited.
Nowadays, the related technology of activating persulfate to degrade organic pollutants by transition metal oxides such as cobalt oxide and copper oxide nanomaterials is rapidly emerging. In addition, a stable two-dimensional sheet structure is generally helpful for the catalyst, and layered double metal oxide (LDO) is gradually favored by researchers as an environment-friendly hydrotalcite-like material with a memory effect. Researches show that the LDO material has the potential for preventing the metal ions of the copper oxide catalyst from dissolving out and keeping the structure stable and good circulation effect when being used as a flaky base material due to adjustable metal components, a layered structure, larger specific surface area, highly dispersed cations in a laminate, strong adsorption performance based on memory effect and alkaline sites and wide catalytic performance. At present, researchers synthesize non-sheet copper oxide materials by a hydrothermal method, a high-temperature calcination method, a loading method and the like to degrade phenolic organic matters, but the synthesis methods are generally complex, for example, a template agent P123 or a high-temperature calcination precursor is used, a high-concentration copper source is generally needed, secondary pollution of an organic reagent is easily introduced, the metal ion elution amount is increased, the material has poor recycling performance, the economy and environmental protection advocated by modern times are not met, and the popularization and the application of the material are not facilitated. Therefore, the method for further exploring the preparation methods of other copper oxide functional materials has important significance.
Disclosure of Invention
The invention aims to provide a green synthesis method of a two-dimensional transition metal nano sheet with structure memory and application thereof, aiming at the defects of the existing preparation method of a flaky transition metal oxide material. The structure memory two-dimensional transition metal nano-sheet material prepared by the invention is used for degrading phenolic pollutants in a multiphase system, has low release amount of harmful metals, low cost and environmental protection, can efficiently remove the phenolic pollutants, provides a simple, convenient and efficient method for treating the phenolic pollutants, has good economic and environmental benefits, and can be produced and applied in a large scale.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a two-dimensional transition metal nano sheet with structure memory comprises the following steps: completely dissolving magnesium salt and aluminum salt in deionized water, dropwise adding ammonia water to adjust the pH to be 9-10, uniformly stirring, centrifugally washing, freeze-drying and calcining to obtain the magnalium layered double metal oxide (LDO) with the memory effect, wherein the magnalium layered double metal oxide is used for uniformly adsorbing copper ions and then is calcined again to obtain the structural memory two-dimensional transition metal nanosheet.
Specifically, the preparation method of the structure memory two-dimensional transition metal nano sheet material comprises the following steps:
(1) dissolving magnesium and aluminum salt in a deionized water solution, stirring at room temperature until the solid is completely dissolved, and preparing an ionic solution with the concentration ratio of magnesium ions to aluminum ions being 2-3 (the ratio of the magnesium ions to the aluminum ions is 2-3: 1); the magnesium salt and the aluminum salt are chloride or nitrate;
(2) dropping the ionic solution prepared in the step (1) and ammonia water into a beaker, adjusting the pH = 9-10 of the mixed solution through the ammonia water, uniformly stirring, standing and aging for 2-6 h;
(3) removing supernatant from the aged solution obtained in the step (2), centrifugally separating, washing, and freeze-drying overnight until water is completely volatilized to obtain white solid magnesium-aluminum layered double hydroxide (LDH precursor);
(4) placing the LDH precursor dried in the step (3) in a muffle furnace, and calcining in an air atmosphere; controlling the heating rate to be 1-10 ℃ per minute-1Calcining at the temperature of 450-600 ℃ for 2-3 h, oxidizing an LDH precursor in the air, removing interlayer water and part of interlayer ions, and obtaining the magnalium layered double metal oxide (LDO) with the memory effect;
(5) preparing a copper ion solution (copper source is copper chloride, copper nitrate or copper sulfate) with the copper ion concentration of 1-600 mg/L, adding the LDO precursor obtained in the step (4) into the copper ion solution for adsorption, and violently stirring for 2-24 hours;
(6) centrifugally washing and drying the solution in the step (5)Drying and calcining in a muffle furnace to obtain a two-dimensional transition metal nano sheet material named c-CuLDO with structure memory; during calcination, the heating rate is 1-10 ℃ per minute-1The calcination temperature is 450-600 ℃, and the heat preservation time is 2-3 h.
According to the technical scheme, the preferable preparation concentration of the ionic solution is 105 mmol/L of magnesium ions and 35 mmol/L of aluminum ions; in the reaction process, the preferable aging time is 3 h; in the drying process, the preferable drying condition is freeze drying; during the calcination, the preferred calcination temperature is 450 ℃, and the preferred calcination time is 3 h; during the adsorption process, the stirring time is preferably 5 h.
The two-dimensional transition metal nano sheet material with the structure memory prepared according to the technical scheme is applied to the treatment of phenolic pollutants, and shows a good removing effect.
The concrete application is as follows: adjusting the pH value of a phenolic pollutant solution to be treated to 9-12, and putting 5-20 mg of two-dimensional transition metal nano-sheets with structure memory into the phenolic pollutant solution, wherein the initial concentration of the phenolic pollutant solution is 1-15 mg/L; and adding 15-30 mg of potassium persulfate to start the reaction, stirring vigorously, and reacting for 20-60 min to complete the degradation of the phenol pollutants.
The material circulation method comprises the following steps: the solid degraded by the appropriate hydrothermal reaction can be used for efficiently degrading the phenol pollutants again; the hydrothermal reaction adopts a hydrothermal kettle with a polytetrafluoroethylene inner container, 5-20 mg of solid is dispersed in 50mL of deionized water, and then the mixture is transferred to a 100 mL hydrothermal kettle; the hydrothermal time is 1 h, and the hydrothermal temperature is 120 ℃.
The invention utilizes LDO material as a substrate, and prepares the LDO two-dimensional memory effect nanosheet material containing copper oxide by a method combining adsorption and calcination without adding any organic reagent, and the LDO two-dimensional memory effect nanosheet material is used for activating persulfate to degrade a multiphase system of phenolic pollutants. The invention overcomes the defects of the traditional template method for preparing the sheet material, uses a low-concentration copper source, has no pollution matrix, and prepares the recyclable phenol pollutant degradation catalyst with high efficiency and low dissolution. The main raw materials and the used equipment are simple and easy to operate, the cost is low, the prepared copper oxide-containing flaky material is environment-friendly, the phenol pollutants in water can be effectively degraded, the economic benefit and the environmental benefit are obvious, and the popularization and application value is good.
The invention has the following remarkable advantages:
(1) the preparation method is green and environment-friendly: the hydrotalcite-like LDH is a material which is easy to artificially synthesize and is similar to natural minerals, can efficiently utilize copper ions in a solution, and realizes the uniform distribution of the copper ions on a two-dimensional sheet; compared with other flaky metal oxides synthesized by a template agent, the method has less environmental pollution, is an ecological environment-friendly preparation method, and the prepared structure memory two-dimensional transition metal nanosheet has a large specific surface area, shows a remarkable effect on treatment of phenolic pollutants, can be recycled, is simple in process operation, low in cost and high in efficiency, and is beneficial to large-scale green production;
(2) the material structure is stable: by utilizing the memory effect of the LDO, the two-dimensional sheet microstructure of the material is kept in the application process, the degradation process is promoted, and the two-dimensional sheet structure cannot be damaged in the degradation process, so that the cyclic utilization of the material is facilitated;
(3) the degradation efficiency is fast: the speed of activating potassium persulfate by the copper-magnesium-aluminum oxide nanosheet material to generate sulfate radical free radicals is high, so that the degradation efficiency is greatly improved, and the applicable pH range is wide;
(4) and (3) low harmful ion dissolution: in the degradation process, compared with the elution amount (0.34 mg/L) of copper ions of a pure copper oxide material, the elution amount of the copper ions of the material is low (less than 0.4 mu g/L) under the same condition.
Drawings
FIG. 1 is an XRD pattern of a two-dimensional transition metal nanoplatelet with structure memory prepared according to example 1 of the present invention; wherein, a) an LDH precursor; b) LDO precursor; c) c-CuLDO;
FIG. 2 is an SEM image of an LDO precursor prepared in example 1 of the present invention;
FIG. 3 is a graph of the change of copper ion adsorption with time of LDO precursor prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a two-dimensional transition metal nanoplatelet with structure memory prepared according to example 1 of the present invention;
FIG. 5 is a graph of the removal rate of phenol contaminant with time for two-dimensional transition metal nanoplatelets with structural memory according to the present invention;
FIG. 6 is a schematic diagram showing the effect of pH on phenol removal efficiency of the two-dimensional transition metal nanosheets with structural memory according to the present invention;
FIG. 7 is a diagram showing the effect of removing phenol from the structural memory two-dimensional transition metal nano-sheet according to the present invention.
Detailed Description
The purpose, technical scheme and advantages of the present application are further described below with reference to the accompanying drawings and embodiments, so that the present application is more clearly described. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Preparing a c-CuLDO structure memory two-dimensional transition metal nano sheet:
(1) dissolving 2.13 g of magnesium chloride hexahydrate and 0.845 g of aluminum chloride hexahydrate in 100 mL of deionized water, and stirring at room temperature until the solid is completely dissolved to prepare a magnesium-aluminum ion solution;
(2) pouring the solution into a 100 mL separating funnel, dropwise adding the solution into a beaker, dropwise adding ammonia water to adjust the pH = 9-10 in the process, adjusting the final pH =9.5 after the dropwise adding is finished, and continuously stirring for 10 minutes;
(3) standing the stirred solution at room temperature, aging for 3 h, removing supernatant, performing centrifugal separation, and washing for 3 times by using deionized water to obtain an LDH precursor;
(4) freeze-drying the LDH precursor for 12 h until the water is completely volatilized;
(5) placing the dried LDH precursor in a muffle furnace, and calcining in an air atmosphere; controlling the heating rate to 2 ℃ and min-1Keeping the temperature at 450 ℃ for 3 h to obtain LDO;
(6) adding LDO into 50mL 60 mg/L cupric chloride solution, stirring for 5 hr, washing, freeze drying, and calcining at 450 deg.C for 3 hr (under control)The heating rate is 2 ℃ and min-1) And obtaining the required c-CuLDO material.
According to example 1, the phases of the LDO precursor before and after calcination and the final c-CuLDO were analyzed by X-ray diffraction, and the X-ray diffraction pattern is shown in FIG. 1. Analysis determined that the LDH phase before calcination was Mg6Al2(OH)18·4.5H2O, the phase of the calcined LDO is MgO, and the phase of the final product c-CuLDO is MgO. Indicating that there is no significant impurity phase and that the copper oxide should be distributed uniformly. The adsorption equilibrium curve for adsorbed copper is shown in fig. 3. Scanning electron microscopes of LDOs and c-CuLDOs are shown in FIGS. 2 and 4. As can be seen from the figure, the sheet structure of the precursor is kept before and after the product is loaded with copper, the sheet grows up, and the structure is more open.
Application example 1
The c-CuLDO nanosheet material obtained in the embodiment 1 is used for removing phenol pollutants, and the specific steps are as follows:
(1) preparation of 10 mg. L-1With NaOH to adjust the solution pH = 11;
(2) putting the prepared c-CuLDO nanosheet material into the phenol solution, and controlling the concentration of the added c-CuLDO to be 0.3 g.L-1Then, the concentration of potassium persulfate to be fed is controlled to be 0.5 g.L-1Stirring vigorously;
(3) and (3) measuring the phenol degradation condition by using high performance liquid chromatography after different time periods, and calculating the removal rate of phenol.
Application example 2
The c-CuLDO nanosheet material obtained in example 1 was used at different pH values to remove phenol contaminants:
(1) preparation of 10 mg. L-1Adjusting the pH value of the solution to 4, 5.6 (without adjustment), 7, 9 and 11 by using HCl or NaOH;
(2) putting the prepared c-CuLDO nanosheet material into the phenol solution, and controlling the concentration of the added c-CuLDO to be 0.3 g.L-1Then, the concentration of potassium persulfate to be fed is controlled to be 0.5 g.L-1Stirring vigorously;
(3) and (3) measuring the phenol degradation condition by using high performance liquid chromatography after different time periods, and calculating the removal rate of phenol.
Inspection of material reusability
(1) Preparation of 10 mg. L-1With NaOH to adjust the solution pH = 11;
(2) putting the prepared c-CuLDO nanosheet material into the phenol solution, and controlling the concentration of the added c-CuLDO to be 0.3 g.L-1Then, the concentration of potassium persulfate to be fed is controlled to be 0.5 g.L-1Stirring vigorously;
(3) and (3) measuring the phenol degradation condition by using high performance liquid chromatography after different time periods, and calculating the removal rate of phenol.
(4) After degradation, centrifuging and washing the sample, putting the sample into a 100 mL high-pressure reaction kettle containing 50mL of water, putting the reaction kettle into a 120-DEG C oven, and preserving heat for 2 hours;
(5) the solution after reaction is cooled along with the furnace, centrifugally separated, washed for 3 times by deionized water, and dried at 60 ℃ to obtain a solid which can be used for degrading phenol with high efficiency again.
FIG. 7 is a graph showing the recycling effect of the c-CuLDO nanosheet material of example 1 as a catalyst for activating persulfate to degrade phenol. It can be seen that the samples without hydrothermal treatment show a performance decrease in the second degradation, but the degradation effect and rate substantially return to the level of the first time of use after hydrothermal treatment. This demonstrates that the c-CuLDO nanosheet material of the present invention can maintain excellent recyclability of the material by a hydrothermal cycling process.
According to application example 1, a phenol removal rate curve as shown in fig. 5 was obtained. As can be seen from FIG. 5, the c-CuLDO nanosheet material caused a continuous decrease in phenol concentration over time. After 20 min, the removal rate of phenol pollutants by the c-CuLDO nanosheet material reaches 99%, the phenol pollutants tend to be balanced after 40 min, and the copper ion elution amount is less than 0.4 mu g/L as measured by inductively coupled plasma mass spectrometry (ICP-MS); however, for the purchased pure CuO powder, the amount of metal eluted after degradation reached 0.34 mg/L, which is about 1000 times that of the c-CuLDO elution. Compared with the c-CuLDO nano sheet material and the pure CuO powder prepared by the invention, the c-CuLDO nano sheet material prepared by the invention has the same performance of removing phenol pollutants as the pure CuO powder, but the metal elution amount is extremely low, the concentration of copper ions used for preparation is also lower, the recycling performance is good, the preparation method is simple, and the method is more economic and environment-friendly.
According to application example 2, a phenol removal rate curve as shown in fig. 6 was obtained. As can be seen from FIG. 6, the c-CuLDO nanosheet material continuously reduced the phenol concentration over time. The c-CuLDO nanosheet material can degrade phenol at a wider pH value, can completely remove phenol within 40 min under alkaline conditions (pH =9 and 11), and can still achieve a removal rate of more than 90% although the degradation rate is reduced under weak acid conditions. Therefore, the c-CuLDO nanosheet material prepared by the method has good stability, keeps activity under most of pH conditions, and is beneficial to wide application.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. The application of two-dimensional transition metal nano-thin sheet with structure memory is characterized in that: the two-dimensional transition metal nano-sheet with the structure memory is used for activating persulfate to degrade phenolic pollutants;
the preparation method of the two-dimensional transition metal nano sheet with the structure memory comprises the following steps:
(1) dissolving 2.13 g of magnesium chloride hexahydrate and 0.845 g of aluminum chloride hexahydrate in 100 mL of deionized water, and stirring at room temperature until the solid is completely dissolved to prepare a magnesium-aluminum ion solution;
(2) pouring the solution into a 100 mL separating funnel, dropwise adding the solution into a beaker, dropwise adding ammonia water to adjust the pH = 9-10 in the process, adjusting the final pH =9.5 after the dropwise adding is finished, and continuously stirring for 10 minutes;
(3) standing the stirred solution at room temperature, aging for 3 h, removing supernatant, performing centrifugal separation, and washing for 3 times by using deionized water to obtain an LDH precursor;
(4) freeze-drying the LDH precursor for 12 h until the water is completely volatilized;
（5）placing the dried LDH precursor in a muffle furnace, and calcining in an air atmosphere; controlling the heating rate to 2 ℃ and min-1Keeping the temperature at 450 ℃ for 3 h to obtain LDO;
(6) adding LDO into 50mL of 60 mg/L copper chloride solution, stirring for 5 h, washing, freeze drying, calcining at 450 deg.C for 3 hr, controlling heating rate at 2 deg.C/min-1And obtaining the required c-CuLDO material.
2. Use according to claim 1, characterized in that: the application specifically comprises the following steps: adjusting the pH value of a phenolic pollutant solution to be treated to 9-12, and putting 5-20 mg of two-dimensional transition metal nano-sheets with structure memory into the phenolic pollutant solution, wherein the initial concentration of the phenolic pollutant solution is 1-15 mg/L; adding 15-30 mg of potassium persulfate to start reaction, stirring vigorously, and reacting for 20-60 min to complete degradation of phenol pollutants; and (3) carrying out hydrothermal reaction on the washed and centrifugally recovered solid to obtain the two-dimensional transition metal nano sheet material for the second degradation.
3. Use according to claim 2, characterized in that: the hydrothermal reaction adopts a hydrothermal kettle with a polytetrafluoroethylene inner container, 5-20 mg of solid is dispersed in 50mL of deionized water, and then the mixture is transferred to a 100 mL hydrothermal kettle; the hydrothermal time is 1 h, and the hydrothermal temperature is 120 ℃.
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| CN104190421A (en) * | 2014-07-30 | 2014-12-10 | 湘潭大学 | Preparation method of Cu-based catalysts capable of highly efficiently degrading azo dyes |
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| CN104190421A (en) * | 2014-07-30 | 2014-12-10 | 湘潭大学 | Preparation method of Cu-based catalysts capable of highly efficiently degrading azo dyes |
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| Heterogeneously catalyzed persulfate by CuMgFe layered double oxide for the degradation of phenol;Yun Chen et al.;《Applied Catalysis A: General》;20170318;第538卷;第19-26页 * |
| 铜基水滑石的构筑及其催化湿式氧化活性;张治青;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20160415(第04期);第10,41,43页 * |
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