CN109748322B - Synthesis method and application of alpha-MnS nano particles and alpha-MnS/rGO composite material - Google Patents
Synthesis method and application of alpha-MnS nano particles and alpha-MnS/rGO composite material Download PDFInfo
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Abstract
The invention provides a synthesis method and application of an alpha-MnS nano particle and an alpha-MnS/rGO composite material, which comprises the following steps: mixing MnCl2·4H2Adding O and thioacetamide into ethylene glycol, stirring, performing ultrasonic treatment, transferring the solution into a polytetrafluoroethylene-lined stainless steel autoclave, and performing sealed heating reaction for 6-14 hours at 190 ℃; and after the reaction is finished, centrifuging, washing and drying to obtain the alpha-MnS nano particles. When graphene oxide is added into the raw materials, the alpha-MnS/rGO composite material can be synthesized. The invention can synthesize pure undoped alpha-MnS nano particles or alpha-MnS/rGO composite materials in one step by a hydrothermal method without annealing reaction. The obtained alpha-MnS nano particles and alpha-MnS/rGO composite material have good third-order nonlinear optical characteristics.
Description
Technical Field
The invention belongs to the technical field of graphene materials, and particularly relates to a synthesis method and application of an alpha-MnS nano particle and alpha-MnS/rGO composite material.
Background
Graphene is a single piece of graphitic carbon, which has great advantages due to its high specific surface area, electrical conductivity, optical, thermal and mechanical properties. Therefore, the graphene has wide application in photoelectric devices, field effect transistors, fuel cells, super capacitors and the like, and the semiconductor composite material generated by compounding the graphene and the inorganic compound also has high application value in optical nonlinear devices, photoelectric devices, photocatalysis and fluorescent labels. In 2010, Cao et al successfully synthesized graphene-CdS quantum dot nanocomposites by a one-step solvothermal method, and demonstrated that there is a ps-level ultrafast electron transfer from CdS quantum dots to graphene substrate (Cao A, Liu ZH, Chu S, et al. A surface one-step method to process graphene-CdS quantum dot nano composites, as a means of formulating optoelectronic Materials [ J ] Advanced Materials, 2010, 22 (1): 103-; li and the like adopt a hydrothermal method to synthesize a gamma manganese sulfide-graphene composite material, and the gamma manganese sulfide-graphene composite material is found to have large specific capacitance and excellent electrochemical performance (Xiao Fu Cu Li, Jian Fu Sn, et al.A.failure of g-MnS/rGO composite by a factor one-point solvent approach for supercapacitors applications [ J ]. Journal of Power Source 282(2015) 194-201); in 2012, Chen et al adopts mercaptopropionic acid to modify CdSe quantum dots, and then compounds the CdSe quantum dots with diallyl dimethyl ammonium chloride modified graphene to prepare a thin-film photovoltaic cell, wherein the photoelectric conversion efficiency reaches 17% (Chen J, Xu F, Wu J, et al. Flexible phosphor cells based on a graphene-CdSe quaternary dot nano composite [ J ]. Nanoscale, 2012,4(2): 441) -443.).
There are many inorganic compounds that can be composited with graphene, and sulfide is one of them. Common sulfides compounded with graphene include manganese sulfide, zinc sulfide, copper sulfide, silver sulfide, cadmium sulfide and the like, and graphene is compounded with the sulfides as an ideal substrate material of the semiconductor quantum dot, so that the performances of the sulfide quantum dot in the aspects of electricity, optics, photocatalysis and the like can be effectively improved. Nanostructured alpha manganese sulfide (α -MnS) is an important material in inorganic semiconductors because of its abundance and ready exploitation. There are three common crystal forms of manganese sulfide: the three crystal forms can be mutually transformed by alpha manganese sulfide, gamma manganese sulfide and beta manganese sulfide. Alpha manganese sulfide of rock salt structure is more stable than gamma manganese sulfide and beta manganese sulfide in crystal form, reaction conditions are easier to control during synthesis, byproducts in products are less, and purity is high.
The Hong ying Quan and the like research a synthesis method of an alpha-MnS/N-rGO composite material: adding Mn (Ac)2﹒4H2O is dissolved in a DMF suspension of GO (graphene oxide); adding L-cysteine aqueous solution to the DMF solution; then the obtained mixed solution reacts for 12 hours in an autoclave at 200 ℃, and the composite material can be obtained. When the reaction raw materials contain no GO, the alpha-MnS nano particles (Quan H, Cheng B, Chen D, et al, One-dot synthesis of alpha-MnS/nitro-reduced graphene oxide hybrid for high-performance enzyme catalysis) with the diameter of 3 μm can be obtained]. Electrochimica Acta, 2016, 210:557-566.）。
A synthesis method of a honeycomb alpha-MnS/NSG composite material is researched by Boli Liu and the like: the GO solution, thiourea and manganese acetate tetrahydrate are uniformly mixed, and then are cracked for 20 hours at 180 ℃ in a polytetrafluoroethylene lining autoclave to obtain colloidal gamma-MnS/NSG, and then are subjected to heat treatment for 4 hours at 600 ℃ in argon to convert the gamma-MnS/NSG into alpha-MnS/NSG. If only the honeycomb alpha-MnS and N-S co-doped rGO is prepared, no GO is added into the precursor solution (Liu B, Liu Z, Li D, et al, Nanoscale alpha-MnS crystallites grow on N-S co-doped rGO as a long-life and high-capacity anode material of Li-ion batteries [ J ]. APPLID SURFACCE SCIENCE, 2017, 416: 858-. The method is utilized to prepare gamma-MnS/NSG firstly, and then the gamma-MnS/NSG is converted into alpha-MnS/NSG through annealing, but the alpha-MnS/NSG is not directly synthesized.
Guanggao Zhang et al studied a hydrothermal synthesis method of γ -MnS/RGO complex: mixing GO and MnCl2·4H2O、Na2S·9H2Heating O in an autoclave at 180 ℃ for 12 hours to obtain the gamma-MnS/RGO compound. When GO does not exist in the raw materials of the reaction, gamma-MnS (Zhang G, Kong M, Yao Y, et al, One-pot synthesis of gamma-MnS/reduced graphene oxide with enhanced performance for aqueous asymmetric superparameters [ J]Nanotechnology, 2017, 28(6): 065402). The final product obtained by the method under the reaction raw materials and the reaction conditions is also gamma-MnS or gamma-MnS/RGO, and if alpha-MnS or alpha-MnS/RGO is further obtained, an annealing process is needed.
Disclosure of Invention
The alpha-MnS and alpha-MnS/rGO composite material is synthesized by a one-step hydrothermal method, and the obtained alpha-MnS and alpha-MnS/rGO nano composite material can be used as a three-order nonlinear optical material.
The invention provides a synthesis method of alpha-MnS nano particles, which comprises the following steps:
step 1: mixing MnCl2·4H2Adding O and thioacetamide into ethylene glycol, stirring and ultrasonically treating, transferring the solution into a polytetrafluoroethylene-lined stainless steel autoclave, and hermetically heating and reacting for 6-14 hours at 190 ℃;
step 2: and after the reaction is finished, centrifuging, washing and drying. The diameter range of the prepared alpha-MnS nano particles is 40-200 nm.
Further, the MnCl in step 12·4H2The molar mass ratio of O to thioacetamide is 1: 3-4.
Further, the volume of ethylene glycol and MnCl in step 12·4H2The molar mass ratio of O is 8ml to 1 mmol.
The alpha-MnS nano particles synthesized by the method can be used as a third-order nonlinear optical material.
Further, the diameter of the alpha-MnS nano particles is 40-200 nm.
When graphene oxide is added into the reaction raw materials, the reaction can be carried out to generate an alpha-MnS/rGO composite material, which specifically comprises the following steps:
step 1: adding graphene oxide into ethylene glycol, and performing ultrasonic dispersion to obtain a suspension;
step 2: adding MnCl into the suspension obtained in the step 12·4H2Stirring and ultrasonically treating O and thioacetamide, transferring the obtained mixed solution into a polytetrafluoroethylene lining stainless steel autoclave, and carrying out sealed heating reaction for 6-14 h at 190 ℃;
and step 3: and after the reaction is finished, centrifuging, washing and drying to obtain the alpha-MnS/rGO composite material, wherein the alpha-MnS in the composite material is in a nano particle structure and is uniformly distributed on the surface of the reduced graphene oxide.
Further, the MnCl in the step 22·4H2The molar mass ratio of O to thioacetamide is 1: 3-4.
Further, the volume of the ethylene glycol is related to MnCl2·4H2The molar mass ratio of O is 8ml to 1 mmol.
The graphene oxide is prepared by adopting an improved typical hammering method and taking natural graphite powder as a raw material, and the method comprises the following steps:
a. weighing graphite powder, putting into a beaker, and adding a proper amount of KMnO4Flattening the mixture;
b. adding phosphoric acid into concentrated sulfuric acid, adding the mixed acid liquid into a three-neck flask in an oil bath kettle, setting the temperature of the oil bath kettle at 50 ℃, and continuously stirring;
c. b, slowly adding the mixture flattened in the step a into a three-neck flask, and reacting for 24 hours after the addition is finished;
d. the ice-water mixture was prepared several hours in advance: the ice-water mixture was prepared by stirring 40ml of hydrogen peroxide and 160ml of deionized water at 0 ℃. And c, adding the mixture obtained by the reaction in the step c into the ice water mixture, continuously stirring, washing by using a high-speed centrifuge at the rotating speed of 12000r/min by using dilute hydrochloric acid, deionized water and absolute ethyl alcohol sequentially after stirring is finished, and finally drying for 8 hours at the temperature of 50 ℃.
The alpha-MnS/rGO composite material synthesized by the method can be used as a third-order nonlinear optical material.
Further, the diameter of the alpha-MnS nano particles on the alpha-MnS/rGO composite material is 65-163 nm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention can synthesize pure undoped alpha-MnS nano particles or alpha-MnS/rGO composite materials in one step by a hydrothermal method without annealing reaction. The small-size alpha-MnS quantum dot is a material with high nonlinear polarizability, and can be used for preparing laser devices.
2. The diameter range of the alpha-MnS nano particles prepared by the invention is 40-200 nm, and the diameter of the alpha-MnS nano particles on the alpha-MnS/rGO composite material is 65-163 nm. In the preparation of pure alpha-MnS, gamma-MnS is first generated which is less stable than alpha-MnS; due to the high temperature for a long time, the gamma-MnS is converted into the alpha-MnS, and the longer the time is, the more thorough the conversion is, and the smaller the particle diameter is. In the preparation of the alpha-MnS/rGO composite material, because a large amount of oxygen-containing groups are arranged on the surface of the graphene oxide, the graphene oxide is reduced at high temperature and high pressure, so that sulfur ions and manganese ions directly generate alpha-MnS on the surface of the reduced graphene oxide, and the longer the time is, the larger the particle diameter is.
3. The three-order nonlinear optical characteristics of the alpha-MnS/rGO composite material under the action of laser with the wavelength of 532nm and the pulse width of 30ps are researched by utilizing a single-beam z-scanning technology, and the result shows that the alpha-MnS/rGO composite material has the three-order nonlinear optical characteristics which are greatly improved compared with the alpha-MnS quantum dots.
Drawings
FIG. 1 is an XRD pattern (left) and an ultraviolet-visible absorption pattern (right) for α -MnS, example 7 GO, rGO and α -MnS/rGO composites made according to example 2 of the present invention.
Fig. 2 is an SEM image of α -MnS nanoparticles prepared in example 1 of the present invention.
Fig. 3 is an SEM image of α -MnS nanoparticles prepared in example 2 of the present invention.
Fig. 4 is an SEM image of α -MnS nanoparticles prepared in example 3 of the present invention.
Fig. 5 is an SEM image of α -MnS nanoparticles prepared in example 4 of the present invention.
Fig. 6 is an SEM image of α -MnS nanoparticles prepared in example 5 of the present invention.
FIG. 7 is an SEM image of an alpha-MnS/rGO composite material prepared in example 6 of the invention.
FIG. 8 is an SEM image of an alpha-MnS/rGO composite material prepared in example 7 of the present invention.
FIG. 9 is an SEM image of an alpha-MnS/rGO composite material prepared in example 8 of the present invention.
FIG. 10 is an SEM image of an alpha-MnS/rGO composite material prepared in example 9 of the present invention.
FIG. 11 is an SEM image of an alpha-MnS/rGO composite material prepared in example 10 of the present invention.
FIG. 12 is a Fourier infrared (left) and Raman (right) plot of α -MnS, example 7 GO and α -MnS/rGO composites made according to the invention, example 2.
FIG. 13 is a Z-scan of the open pores of α -MnS prepared in example 2 of the present invention.
FIG. 14 is a closed/open Z-scan of α -MnS made in accordance with example 2 of the present invention.
FIG. 15 is a Z-scan of the open pores of the α -MnS/rGO composite material prepared in example 7 of the present invention.
FIG. 16 is a closed/open cell Z scan of α -MnS/rGO prepared in example 2 of the invention.
Detailed Description
Example 1
The synthesis method of the alpha-MnS nano particles comprises the following specific steps:
1.97g (0.01 mol) of MnCl2·4H2Adding O and 2.48g (0.033 mol) thioacetamide into 80ml ethylene glycol, stirring (1000 rpm) for 1h, performing ultrasonic treatment for 2h, transferring the solution into two stainless steel autoclaves with 50ml polytetrafluoroethylene linings, performing sealed heating reaction at 190 ℃ for 6h, centrifuging under the condition of 10000r/min after the reaction is finished, washing with absolute ethyl alcohol for 3 times, washing with ultrapure water for 3 times, and drying for 24h by using a blast dryer; the alpha-MnS nano-particles with the diameter of about 200nm are obtained, as shown in figure 2.
Example 2
The present example is basically the same as example 1, and the details of the same parts are not repeated, except that the reaction time is 8 h; finally, the alpha-MnS nano-particles with the diameter of about 100nm are obtained, as shown in figure 3.
Example 3
The present example is basically the same as example 1, and the details of the same parts are not repeated, except that the reaction time is 10 hours; finally, the alpha-MnS nano-particles with the diameter of about 80nm are obtained, as shown in figure 4.
Example 4
The present example is basically the same as example 1, and the details of the same parts are not repeated, except that the reaction time is 12 h; finally, the alpha-MnS nano-particles with the diameter of about 50nm are obtained, as shown in figure 5.
Example 5
The present example is basically the same as example 1, and the details of the same parts are not repeated, except that the reaction time is 14 h; finally, the alpha-MnS nano particles with the diameter of about 40nm are obtained, as shown in figure 6.
Example 6
The synthesis method of the alpha-MnS/rGO comprises the following specific steps:
step 1: adding 60mg of graphene oxide into 80ml of ethylene glycol, and performing ultrasonic dispersion for 2 hours to obtain a suspension;
step 2: 1.97g of MnCl was added to the suspension obtained in step 12·4H2O and 2.48g thioacetamide are stirred (1000 revolutions per minute) for 1 hour and subjected to ultrasonic treatment for 2 hours, then the solution is transferred into two 50ml stainless steel autoclaves with polytetrafluoroethylene linings, sealed and heated at 190 ℃ for reaction for 6 hours, after the reaction is finished, the solution is centrifuged at 10000r/min, washed 3 times by absolute ethyl alcohol, washed 3 times by ultrapure water and dried in a blast drier for 24 hours, and the alpha-MnS/rGO composite material with the diameter of about 65nm is obtained, as shown in figure 7.
The graphene oxide is prepared by adopting an improved typical hammering method and taking natural graphite powder as a raw material, and the method comprises the following steps:
a. weighing 0.75g of graphite powder, putting into a beaker, and adding a proper amount of KMnO4Flattening the mixture;
b. adding 10ml phosphoric acid into 90ml concentrated sulfuric acid, adding the mixed acid liquid into a three-neck flask in an oil bath kettle, setting the temperature of the oil bath kettle at 50 ℃, and continuously stirring;
c. b, slowly adding the mixture flattened in the step a into a three-neck flask, and reacting for 24 hours after the addition is finished;
d. the ice-water mixture was prepared several hours in advance: the ice-water mixture was prepared by stirring 40ml of hydrogen peroxide and 160ml of deionized water at 0 ℃. And c, adding the mixture obtained by the reaction in the step c into the ice water mixture, continuously stirring, washing the mixture by using a high-speed centrifuge at a rotating speed of 12000r/min by using dilute hydrochloric acid, deionized water and absolute ethyl alcohol sequentially after stirring is finished, and finally drying the mixture for 8 hours at 50 ℃ to obtain the graphene oxide.
Example 7
The present example is basically the same as example 6, and the details of the same parts are not repeated, except that the reaction time is 8 h; a diameter α -MnS/rGO composite was obtained with α -MnS on the composite having a diameter of about 95nm, as shown in fig. 8.
Example 8
The present example is basically the same as example 6, and the details of the same parts are not repeated, except that the reaction time is 10 hours; a diameter α -MnS/rGO composite was obtained with α -MnS on the composite having a diameter of about 140nm, as shown in fig. 9.
Example 9
The present example is basically the same as example 6, and the details of the same parts are not repeated, except that the reaction time is 12 h; a diameter α -MnS/rGO composite was obtained with α -MnS on the composite having a diameter of about 152nm, as shown in fig. 10.
Example 10
The present example is basically the same as example 6, and the details of the same parts are not repeated, except that the reaction time is 14 h; a diameter α -MnS/rGO composite was obtained with α -MnS on the composite having a diameter of about 163nm, as shown in fig. 11.
The α -MnS nanoparticles and α -MnS/rGO composite prepared in the above examples were characterized using an X-ray diffractometer, a field emission electron microscope, a fourier transform infrared spectrometer, a raman spectrometer and an ultraviolet-visible spectrum, and their structures, diameters, morphologies and absorption characteristics were analyzed, and the results showed:
comparing the characteristic peaks of the alpha-MnS nano particles and the alpha-MnS/rGO in the XRD image shown in figure 1 with JSPDS, the successful synthesis of the target material alpha-MnS nano particles and alpha-MnS/rGO composite material is demonstrated. The features of the raman spectra, fourier infrared spectra and uv-vis absorption spectra in fig. 1 and 12 can further demonstrate that the materials detected are α -MnS and α -MnS/rGO. The SEM images of FIGS. 2 to 6 show that the alpha-MnS is spherical, and the SEM images of FIGS. 7 to 11 show that the alpha-MnS is uniformly compounded on the surface of the reduced graphene oxide.
As shown in fig. 13 to 16, the single beam z-scan technique was used to analyze the third-order nonlinear optical properties of the ethanol solutions (concentration 1.25 mg/ml) of the α -MnS nanoparticles and the α -MnS/rGO composite materials prepared in examples 2 and 7 under the action of laser light with a wavelength of 532nm, a pulse width of 30ps, and an energy of 7 uj. The results show that the alpha-MnS nano particles and the alpha-MnS/rGO composite material both have three-order nonlinear optical characteristics, and the polarizability of the alpha-MnS nano particles is 0.33 multiplied by 10-12
esu, absorption coefficient 0.60X 10-11mW-1The polarizability of the alpha-MnS/rGO composite material is 4.93 multiplied by 10-12esu, suctionThe yield coefficient is-2.21 x 10-11mW-1. Compared with the alpha-MnS quantum dots, the third-order nonlinear characteristic of the alpha-MnS/rGO composite material is greatly improved.
Claims (8)
1. The application of the alpha-MnS nano particles as a three-order nonlinear optical material is characterized in that the synthesis method of the alpha-MnS nano particles comprises the following specific steps:
step 1: mixing MnCl2·4H2Adding O and thioacetamide into ethylene glycol, stirring, performing ultrasonic treatment, transferring the solution into a polytetrafluoroethylene-lined stainless steel autoclave, and performing sealed heating reaction for 6-14 hours at 190 ℃;
step 2: and after the reaction is finished, centrifuging, washing and drying to obtain the alpha-MnS nano particles.
2. Use of α -MnS nanoparticles as claimed in claim 1 as third-order nonlinear optical material, characterized in that in step 1 said MnCl is2·4H2The molar mass ratio of O to thioacetamide is 1: 3-4.
3. Use of α -MnS nanoparticles as claimed in claim 1 as third-order nonlinear optical material, characterized in that the volume of ethylene glycol and MnCl in step 12·4H2The molar mass ratio of O is 8ml:1 mmol.
4. The use of α -MnS nanoparticles as third-order nonlinear optical materials according to claim 1, wherein the α -MnS nanoparticles have a diameter of 40 to 200 nm.
5. The application of the alpha-MnS/rGO composite material as a third-order nonlinear optical material is characterized in that the synthesis method of the alpha-MnS/rGO composite material specifically comprises the following steps:
step 1: adding graphene oxide into ethylene glycol, and performing ultrasonic dispersion to obtain a suspension;
step 2: adding MnCl into the suspension obtained in the step 12·4H2Stirring and ultrasonically treating O and thioacetamide, transferring the obtained mixed solution into a polytetrafluoroethylene lining stainless steel autoclave, and carrying out sealed heating reaction for 6-14 h at 190 ℃;
and step 3: and after the reaction is finished, centrifuging, washing and drying to obtain the alpha-MnS/rGO composite material.
6. Use of an α -MnS/rGO composite material according to claim 5 as third-order nonlinear optical material, characterized in that said MnCl in step 22·4H2The molar mass ratio of O to thioacetamide is 1: 3-4.
7. Use of an alpha-MnS/rGO composite according to claim 5 as a third-order nonlinear optical material, characterized in that the volume of ethylene glycol and MnCl2·4H2The molar mass ratio of O is 8ml:1 mmol.
8. Use of an α -MnS/rGO composite as claimed in claim 5 as a third order nonlinear optical material, characterized in that the α -MnS nanoparticles on said α -MnS/rGO composite have a diameter comprised between 65 and 163 nm.
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