CN110615462B - Method for green synthesis of oil-soluble zinc sulfide quantum dots based on liquid paraffin solvent system - Google Patents
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Abstract
The invention discloses a method for green synthesis of oil-soluble zinc sulfide quantum dots based on a liquid paraffin solvent system, which is characterized in that liquid paraffin is used for replacing an organic solvent, a supergravity reaction strengthening technology, namely a rotary packed bed reactor, is used for preparing the zinc sulfide quantum dots, specifically, zinc-containing metal salt and sodium sulfide nonahydrate are used as a zinc source and a sulfur source, long-chain carboxylic acid is used as a stabilizer, a precursor solution is introduced into a supergravity reactor for nucleation and growth processes, and finally, absolute ethyl alcohol is used for centrifugal separation to obtain the oil-soluble zinc sulfide quantum dots with the size of 2-3 nm. The method has the advantages of simple synthetic process, low cost and environmental protection. The reinforcing process of the super-gravity rotating packed bed is utilized to ensure the uniformity of the product on the basis of greatly shortening the reaction time. In addition, as a continuous reactor, the supergravity rotating packed bed can realize continuous production of products and ensure good repeatability among different batches of products, and has unique advantages for large-scale synthesis of high-quality nano materials.
Description
Technical Field
The invention belongs to the cross technical field of chemical industry, materials and photonics, and relates to a method for green synthesis of oil-soluble zinc sulfide quantum dots based on a liquid paraffin solvent system.
Background
The quantum dots are nano-scale semiconductors, and the particle size is generally 1-10 nm. The semiconductor material as a new generation has the following advantages: 1. by changing the size of the particles, the emission spectrum can be regulated and controlled; 2. the Stokes shift is large, and the light-emitting diode has a narrower emission spectrum and a wider absorption spectrum; 3. high optical stability and good biocompatibility. Based on the advantages, the method has application prospects in biological diagnosis, display, illumination, electronic devices and other aspects. ZnS is a II-VI family wide bandgap direct band gap semiconductor compound, compared with quantum dots containing lead elements and cadmium elements such as PbSe, CdTe and the like, the ZnS quantum dots have the advantages of rich raw materials, economy, low toxicity, no environmental pollution and important application in various fields, and in addition, the ZnS is a wide bandgap semiconductor luminescent material with excellent performance. At present, the synthesis method of ZnS quantum dots mainly comprises a water-phase coprecipitation method, a sol-gel method, a microemulsion method and the like. However, the methods have obvious disadvantages, namely, high-temperature and high-pressure operation conditions, toxic and harmful reaction reagents; secondly, the preparation process is complicated, the repeatability among batches is poor, the yield is low, and the industrial production of the product is not facilitated. Therefore, the method has important significance for preparing the ZnS quantum dots by adopting simple and easily obtained reaction raw materials and finding a simple and feasible synthesis method.
In conventional organic synthesis, organic solvents are the most commonly used reaction media, but the toxicity and difficulty in recovery of organic solvents make them environmentally harmful. The liquid paraffin mainly comprises n-alkane with 8-24 carbon atoms. Firstly, the n-alkane has no branch chain, so the liquid paraffin has extremely low polarity and can be used as a non-polar solvent; and the n-alkane has no unsaturated double bond, stable property and boiling point of over 300 ℃. Finally, the liquid paraffin is odorless and tasteless at room temperature, has almost no toxic action on human bodies, has wide medical application, good safety and low price, and is an ideal replacement solvent in the process of synthesizing optical nano materials.
Hypergravity refers to the acceleration of gravity of the earth in the ratio of 9.8m/s2) Much greater forces are experienced by the material in the environment. Under the environment of supergravity, the process of molecular diffusion and interphase mass transfer between molecules with different sizes is much faster than that under the conventional gravity field, and liquid is torn into micron-to-nano-scale liquid films, liquid threads and liquid drops under huge shearing force to generate huge and fast updated phase interfaces, promote coalescence and separation of two phases and greatly improve the transmission speed between phases. The hypergravity technology can be realized by a hypergravity device, a typical hypergravity device is a rotating packed bed, and researches show that in the rotating packed bed reactorThe mixing characteristic time of the molecules is less than the nucleation induction time, so that the nucleation process is carried out in a microcosmic uniform environment and is controllable, and the rapid update of a phase interface can hinder the growth of crystal nuclei to finally generate small-size nanoparticles. The application of the supergravity technology to the preparation of ZnS quantum dots has the following advantages:
(1) the method utilizes the liquid paraffin as a reaction medium to prepare the ZnS quantum dot for the first time. The ZnS quantum dots prepared in the past are mostly carried out in volatile organic media with high toxicity, and the reaction reagent is expensive and harmful to the environment. The liquid paraffin is used as normal paraffin, the boiling point can reach 300 ℃, the VOC content in the environment is reduced, but the liquid viscosity is higher, the mass transfer resistance is more obvious in a common reactor, the concentration distribution of reactants is not uniform in the reaction process, and the prepared product is easy to agglomerate, so that the preparation of the quantum dots with uniform particle size by using the liquid paraffin as a reaction medium is always a challenge. Under the condition of supergravity, the supergravity reactor is under the condition of supergravity, and due to the existence of huge acceleration, the liquid is split into extremely small liquid drops under the condition of violent collision, strong micromixing is carried out between reactants, and the phase interface is quickly updated, so that the interphase mass transfer process is greatly enhanced, and the supergravity reactor has unique advantages for reaction media with large viscosity. Therefore, the preparation of uniform products can be realized in a liquid paraffin system through a supergravity reactor, the particle size of the products can be below 2nm, and the products can be stably dispersed in a non-polar organic solvent.
(2) The invention can realize the large-scale industrialized production of the quantum dots. For fast reaction synthesized quantum dots, reaction process control parameters such as temperature, stirring rate, precursor injection location and mixing are critical to the quality of the final product, however, it is difficult to fully control reaction parameters and conditions in conventional batch reactors, especially when large amounts of solution are involved. An alternative to a batch reactor is a continuous reactor, with a high gravity reactor as a continuous reactor, allowing for continuous feed of reactants into the reactor and exit as a continuous product. Since the reaction parameters (e.g., residence time, temperature and pressure) are better controlled than batch operations, the product quality is more consistent and has great potential for industrial production of quantum dots.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel method for green synthesis of oil-soluble zinc sulfide quantum dots by using a supergravity strengthening technology. Compared with the prior art, the following beneficial effects can be achieved:
the method for green synthesis of the oil-soluble zinc sulfide quantum dots based on the liquid paraffin solvent system has the advantages of short reaction time, simple operation process, low environmental requirement of the preparation process and low cost of required equipment and raw materials.
The method for green synthesis of the oil-soluble zinc sulfide quantum dots based on the liquid paraffin solvent system has the advantages that the used solvent is low in price and environment-friendly, the problems of large liquid viscosity and poor mass transfer effect are solved by using the supergravity reactor, and the prepared product is uniform in particle size distribution, has the particle size below 2nm and can be stably dispersed in a non-polar organic solvent.
The method for green synthesis of the oil-soluble zinc sulfide quantum dots based on the liquid paraffin solvent system can realize continuous production of products by using the supergravity reactor, overcomes the problems of poor batch repeatability and inconsistent product quality caused by using an intermittent kettle type reactor in the traditional preparation process, and is beneficial to large-scale industrial production.
The technical scheme adopted by the invention is a method for green synthesis of oil-soluble zinc sulfide quantum dots based on a liquid paraffin solvent system, the method comprises the steps of taking zinc-containing metal salt, sodium sulfide nonahydrate as a zinc source and a sulfur source, taking long-chain carboxylic acid as a stabilizer, introducing a precursor solution into a supergravity reactor for nucleation and growth, and finally carrying out centrifugal separation by using absolute ethyl alcohol to obtain the oil-soluble zinc sulfide quantum dots with the size of 2-3 nm.
The preparation method comprises the following steps:
s1, preparing a zinc precursor oil phase solution: adding zinc-containing metal salt into liquid paraffin, purging in nitrogen atmosphere for 20 minutes, adding a certain amount of long-chain carboxylic acid, heating and stirring at a certain temperature to obtain clear and transparent zinc precursor oil phase solution;
s2, preparing a sulfur precursor aqueous phase solution: adding a certain amount of emulsifier into sodium sulfide nonahydrate serving as a sulfur source, and oscillating and dissolving the mixture in ultrapure water to obtain a sulfur precursor water phase solution;
s3, simultaneously introducing the zinc precursor oil phase solution prepared in the S1 and the sulfur precursor water phase solution prepared in the S2 into a supergravity external circulation reactor through a peristaltic pump, and performing nucleation and growth processes in a supergravity environment;
s4, after nucleation and growth are completed, introducing a mixed solution of a zinc precursor oil phase solution and a sulfur precursor water phase solution and ethanol into the supergravity reactor again through two feeding paths for demulsification, then washing an obtained product with absolute ethyl alcohol, removing redundant surfactant, finally placing the product in a drying oven at 60 ℃, drying for 5-10 h, cooling to room temperature to obtain a solid product, wherein the solid product is solidified oil-soluble zinc sulfide quantum dots;
s5, adding the solid product obtained in the step S4 into a dispersion solvent, and performing ultrasonic treatment to obtain the zinc sulfide nano dispersion capable of being stably dispersed in an organic phase.
The concentration of the zinc precursor oil phase solution in S1 is 10 mmol/L-100 mmol/L, the adding amount ratio of the liquid paraffin and the long-chain carboxylic acid is (5-10): 1, wherein the zinc-containing metal salt is one or more of anhydrous zinc acetate, dihydrate zinc acetate, zinc perchlorate or zinc stearate, and the long-chain carboxylic acid is one or more of oleic acid, myristic acid, lauric acid or stearic acid.
The concentration of the aqueous phase solution of the sulfur precursor in S2 is 10 mmol/L-100 mmol/L, wherein the emulsifier comprises one or more of Tween20, Tween80, Span20, Span80, PVP or SDS.
The rotating speed of the super-gravity reactor in the S3 is 500-2500 rpm.
The dispersant in S5 comprises one of cyclohexane, n-hexane, toluene or chloroform.
The method of the invention utilizes an external circulation type hypergravity rotating packed bed to prepare the oil-soluble zinc sulfide quantum dots, and the analysis of a Transmission Electron Microscope (TEM) and an X-ray diffraction (XRD) shows that: compared with the traditional preparation method, the technical process of the invention utilizes the supergravity reactor to overcome the defects of large viscosity and poor mass transfer effect of the liquid paraffin, and the ZnS quantum dots with good dispersibility and a cubic crystal structure are prepared, and the product can be stably dispersed in a nonpolar organic solvent. The liquid paraffin is used as a reaction medium, so that the reaction process is more environment-friendly, the particle size distribution of the prepared product is more uniform, and the particle size is below 2 nm.
Drawings
Fig. 1 is a diffraction (XRD) spectrum of the prepared ZnS quantum dot.
Fig. 2 is a Transmission Electron Microscope (TEM) photograph of the prepared ZnS quantum dots.
Fig. 3 is a High Resolution Transmission Electron Microscope (HRTEM) photograph of the prepared ZnS quantum dots.
Fig. 4 is an energy spectrum (EDS) elemental analysis of the prepared ZnS quantum dots.
Fig. 5 is a photograph of a dispersion of the prepared ZnS quantum dots.
Fig. 6 is a Transmission Electron Microscope (TEM) and a dispersion photograph of the prepared ZnSs quantum dots.
Detailed Description
Example 1
50mL of liquid paraffin is measured into a 250mL three-neck flask, 0.8g of zinc acetate dihydrate is added, 5mL of oleic acid is added after purging for 20 minutes under nitrogen, and the mixture is heated to 60 ℃ under stirring to react for 20 minutes to obtain a clear and transparent zinc precursor oil phase solution which is marked as solution A. 25mL of ultrapure water was weighed into a 100mL beaker, and 0.25g of sodium sulfide nonahydrate and 1mL of Tween-20 were added thereto and dissolved by shaking, and the solution was designated as solution B. Adjusting the rotating speed of the external circulation type hypergravity rotating packed bed to 1000rpm, introducing A, B solution into the external circulation type hypergravity rotating packed bed through a peristaltic pump, setting the feeding flow rate of the solution A and the solution B to be 1:1, and immediately collecting the discharged solution after all the raw material solution is introduced into the external circulation type hypergravity rotating packed bed. And introducing the discharged solution and absolute ethyl alcohol into the rotary packed bed again through two feeding paths to perform demulsification for 5 minutes, washing and purifying the obtained product for 3 times by using the absolute ethyl alcohol, drying the product for 8 hours at the temperature of 60 ℃ in a drying oven, and dispersing the product into cyclohexane to obtain the oil-soluble silver sulfide quantum dot dispersoid.
Example 2
50mL of liquid paraffin is measured into a 250mL three-neck flask, 0.7g of zinc acetate dihydrate is added, after purging for 20 minutes under nitrogen, 2.5mL of oleic acid is added, and the mixture is heated to 80 ℃ under stirring to react for 20 minutes to obtain a clear and transparent zinc precursor oil phase solution, which is marked as solution A. 50ml of ultrapure water was weighed into a 100ml beaker, and 0.3g of sodium sulfide nonahydrate and 1g of SDS were added thereto and dissolved by shaking, and the solution was designated as solution B. Adjusting the rotating speed of the external circulation type hypergravity rotating packed bed to 1000rpm, introducing A, B solution into the external circulation type hypergravity rotating packed bed through a peristaltic pump, setting the feeding flow rate of the solution A and the solution B to be 1:1, introducing all raw material solution into the external circulation type hypergravity rotating packed bed, circulating for 5 minutes, and collecting discharged solution. And introducing the discharged solution and absolute ethyl alcohol into the rotary packed bed again through two feeding paths to perform demulsification for 5 minutes, washing and purifying the obtained product for 3 times by using the absolute ethyl alcohol, drying the product for 8 hours at the temperature of 60 ℃ in a drying oven, and dispersing the product into cyclohexane to obtain the oil-soluble silver sulfide quantum dot dispersoid.
Example 3
50mL of liquid paraffin is measured into a 250mL three-neck flask, 0.8g of zinc stearate is added, after purging for 20 minutes under nitrogen, 5mL of oleic acid is added, and the mixture is heated to 60 ℃ under stirring to react for 20 minutes to obtain a clear and transparent zinc precursor oil phase solution which is marked as solution A. 50mL of ultrapure water was weighed into a 100mL beaker, and 0.5g of sodium sulfide nonahydrate and 1mL of Tween-20 were added thereto and dissolved by shaking to obtain a solution B. Adjusting the rotating speed of the external circulation type hypergravity rotating packed bed to 2000rpm, introducing A, B solution into the external circulation type hypergravity rotating packed bed through a peristaltic pump, setting the feeding flow rate of the solution A and the solution B to be 1.5:1, introducing all raw material solution into the external circulation type hypergravity rotating packed bed, circulating for 10 minutes, and collecting discharged material solution. And introducing the discharged solution and absolute ethyl alcohol into the rotary packed bed again through two feeding paths to perform demulsification for 5 minutes, washing and purifying the obtained product for 3 times by using the absolute ethyl alcohol, drying the product for 8 hours at the temperature of 60 ℃ in a drying oven, and dispersing the product into cyclohexane to obtain the oil-soluble silver sulfide quantum dot dispersoid.
Example 4
100mL of liquid paraffin is measured into a 250mL three-neck flask, 1.5g of zinc stearate is added, 10mL of oleic acid is added after the three-neck flask is purged for 20 minutes under nitrogen, and the three-neck flask is heated to 80 ℃ under the stirring condition to react for 20 minutes to obtain a clear and transparent zinc precursor oil phase solution which is marked as solution A. 100ml of ultrapure water was weighed into a 100ml beaker, and 0.8g of sodium sulfide nonahydrate and 1g of SDS were added thereto and dissolved by shaking, and the solution was designated as solution B. Adjusting the rotating speed of the external circulation type hypergravity rotating packed bed to 2500rpm, introducing A, B solution into the external circulation type hypergravity rotating packed bed through a peristaltic pump, setting the feeding flow rate of the solution A and the solution B to be 1.2:1, introducing all raw material solution into the external circulation type hypergravity rotating packed bed, circulating for 30 minutes, and collecting discharged material solution. And introducing the discharged solution and absolute ethyl alcohol into the rotary packed bed again through two feeding paths to perform demulsification for 5 minutes, washing and purifying the obtained product for 3 times by using the absolute ethyl alcohol, drying the product for 8 hours at the temperature of 60 ℃ in a drying oven, and dispersing the product into cyclohexane to obtain the oil-soluble silver sulfide quantum dot dispersoid.
Example 5
100mL of liquid paraffin is measured into a 250mL three-neck flask, 1.5g of zinc stearate is added, 5mL of oleic acid and 5mL of oleylamine are added after purging for 20 minutes under nitrogen, and the mixture is heated to 80 ℃ under stirring to react for 20 minutes to obtain a clear and transparent zinc precursor oil phase solution which is marked as solution A. 100ml of ultrapure water was weighed into a 100ml beaker, and 0.8g of sodium sulfide nonahydrate, 0.5g of SDS and 0.5g of PVP were added and dissolved by shaking, and the solution was recorded as solution B. Adjusting the rotating speed of the external circulation type hypergravity rotating packed bed to 2500rpm, introducing A, B solution into the external circulation type hypergravity rotating packed bed through a peristaltic pump, setting the feeding flow rate of the solution A and the solution B to be 1:1, introducing all raw material solution into the external circulation type hypergravity rotating packed bed, circulating for 1 hour, and collecting discharged solution. And introducing the discharged solution and absolute ethyl alcohol into the rotary packed bed again through two feeding paths to perform demulsification for 5 minutes, washing and purifying the obtained product for 3 times by using the absolute ethyl alcohol, drying the product for 8 hours at the temperature of 60 ℃ in a drying oven, and dispersing the product into cyclohexane to obtain the oil-soluble silver sulfide quantum dot dispersoid.
Example 6
100mL of liquid paraffin is measured into a 250mL three-neck flask, 2.0g of zinc acetate dihydrate is added, 10mL of oleic acid is added after purging for 20 minutes under nitrogen, and the mixture is heated to 80 ℃ under stirring to react for 20 minutes to obtain a clear and transparent zinc precursor oil phase solution which is marked as solution A. 100mL of ultrapure water was weighed into a 100mL beaker, 2.4g of sodium sulfide nonahydrate and 2mL of Tween-20 were added, and the mixture was dissolved by shaking and recorded as solution B. Adjusting the rotating speed of the external circulation type hypergravity rotating packed bed to 1500rpm, introducing A, B solution into the external circulation type hypergravity rotating packed bed through a peristaltic pump, setting the feeding flow rate of the solution A and the solution B to be 1:1, and immediately collecting the discharged solution after all the raw material solution is introduced into the external circulation type hypergravity rotating packed bed. And introducing the discharged solution and absolute ethyl alcohol into the rotary packed bed again through two feeding paths to perform demulsification for 5 minutes, washing and purifying the obtained product for 3 times by using the absolute ethyl alcohol, drying the product for 8 hours at the temperature of 60 ℃ in a drying oven, and dispersing the product into cyclohexane to obtain the oil-soluble silver sulfide quantum dot dispersoid.
Example 7
50mL of liquid paraffin was weighed into a 250mL three-necked flask, 1.0g of zinc stearate was added, after purging under nitrogen for 20 minutes, 2.5mL of oleic acid was added, and the mixture was heated to 60 ℃ with stirring to react for 20 minutes, yielding a clear and transparent zinc precursor oil phase solution, denoted as solution A. 100mL of ultrapure water was weighed into a 100mL beaker, and 0.4g of sodium sulfide nonahydrate and 1mL of Tween-20 were added thereto and dissolved by shaking, and the solution was designated as solution B. Adjusting the rotating speed of the external circulation type hypergravity rotating packed bed to 500rpm, introducing A, B solution into the external circulation type hypergravity rotating packed bed through a peristaltic pump, setting the feeding flow rate of the solution A and the solution B to be 1:1, and immediately collecting the discharged solution after all the raw material solution is introduced into the external circulation type hypergravity rotating packed bed. And introducing the discharged solution and absolute ethyl alcohol into the rotary packed bed again through two feeding paths to perform demulsification for 5 minutes, washing and purifying the obtained product for 3 times by using the absolute ethyl alcohol, drying the product for 8 hours at the temperature of 60 ℃ in a drying oven, and dispersing the product into cyclohexane to obtain the oil-soluble silver sulfide quantum dot dispersoid.
Claims (2)
1. A method for green synthesis of oil-soluble zinc sulfide quantum dots based on a liquid paraffin solvent system comprises the steps of taking zinc-containing metal salt and sodium sulfide nonahydrate as a zinc source and a sulfur source, taking long-chain carboxylic acid as a stabilizer, introducing a precursor solution into a supergravity reactor for nucleation and growth, and finally carrying out centrifugal separation by using absolute ethyl alcohol to obtain the oil-soluble zinc sulfide quantum dots; the method is characterized in that:
the implementation process of the method comprises the following steps:
s1, preparing a zinc precursor oil phase solution: adding zinc-containing metal salt into liquid paraffin, purging in nitrogen atmosphere for 20 minutes, adding a certain amount of long-chain carboxylic acid, heating and stirring at a certain temperature to obtain clear and transparent zinc precursor oil phase solution;
s2, preparing a sulfur precursor aqueous phase solution: adding a certain amount of emulsifier into sodium sulfide nonahydrate serving as a sulfur source, and oscillating and dissolving the mixture in ultrapure water to obtain a sulfur precursor water phase solution;
s3, simultaneously introducing the zinc precursor oil phase solution prepared in the S1 and the sulfur precursor water phase solution prepared in the S2 into the hypergravity external circulation reactor through a peristaltic pump, and performing nucleation and growth processes in a hypergravity environment;
s4, after nucleation and growth are completed, introducing a mixed solution of a zinc precursor oil phase solution and a sulfur precursor water phase solution and ethanol into the supergravity reactor again through two feeding paths for demulsification, then washing an obtained product with absolute ethyl alcohol, removing redundant surfactant, finally placing the product in a drying oven at 60 ℃, drying for 5-10 h, and cooling to room temperature to obtain a solid product, wherein the solid product is solidified oil-soluble zinc sulfide quantum dots;
s5, adding the solid product obtained in the step S4 into a dispersing solvent, and performing ultrasonic treatment to obtain a zinc sulfide nano dispersion capable of being stably dispersed in an organic phase;
the concentration of the zinc precursor oil phase solution in S1 is 10 mmol/L-100 mmol/L, the adding amount ratio of the liquid paraffin and the long-chain carboxylic acid is (5-10): 1, wherein the zinc-containing metal salt is one or more of anhydrous zinc acetate, dihydrate zinc acetate, zinc perchlorate or zinc stearate, and the long-chain carboxylic acid is one or more of oleic acid, myristic acid, lauric acid or stearic acid;
the concentration of the aqueous phase solution of the sulfur precursor in S2 is 10 mmol/L-100 mmol/L, and the emulsifier comprises one or more of Tween20, Tween80, Span20, Span80, PVP or SDS;
the dispersing solvent in S5 comprises one of cyclohexane, n-hexane, toluene or chloroform.
2. The method for green synthesis of the oil-soluble zinc sulfide quantum dots based on the liquid paraffin solvent system according to claim 1, wherein the method comprises the following steps: the rotating speed of the super-gravity reactor in the S3 is 500-2500 rpm.
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