CN107572489B - Zinc selenide ultrathin nanobelt and anion exchange method for preparing same - Google Patents
Zinc selenide ultrathin nanobelt and anion exchange method for preparing same Download PDFInfo
- Publication number
- CN107572489B CN107572489B CN201710668586.2A CN201710668586A CN107572489B CN 107572489 B CN107572489 B CN 107572489B CN 201710668586 A CN201710668586 A CN 201710668586A CN 107572489 B CN107572489 B CN 107572489B
- Authority
- CN
- China
- Prior art keywords
- ultrathin
- nanobelt
- zinc selenide
- zinc
- diethylenetriamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention provides a porous zinc selenide ultrathin nanobelt and a preparation method thereof by adopting an anion exchange method, wherein the porous zinc selenide ultrathin nanobelt is of an ultrathin belt-shaped structure with the length of 5-10 mu m, the width of 17-19nm and the thickness of less than 5nm, and the surface of the ultrathin nanobelt is of an obvious porous structure. In addition, the invention also takes the prepared porous zinc selenide ultrathin nanobelt as a raw material, and further provides a zinc selenide/molybdenum disulfide heterogeneous nanobelt and a preparation method thereof. The zinc selenide nanobelt prepared by the invention has good water solubility and dispersibility and good photocatalytic activity for hydrogen production by light, and the prepared molybdenum disulfide with a heterostructure further remarkably improves the photocatalytic performance.
Description
Technical Field
The invention belongs to the field of preparation of nano materials, and particularly relates to a zinc selenide ultrathin nanobelt and an anion exchange method for preparing the zinc selenide ultrathin nanobelt, and a corresponding zinc selenide/molybdenum disulfide heterogeneous nanobelt is prepared by taking the zinc selenide ultrathin nanobelt as a precursor.
Background
Zinc sulfide as an important II-VI semiconductor material has a wide development prospect and application potential in the fields of electrocatalysis, photocatalysis, electroluminescence and the like, and has attracted the research interest of scientists. However, in the field of photo-hydrogen production, the zinc sulfide with too wide band gap (-3.7 eV) cannot be utilized by visible light, so that the sunlight utilization rate is low, and the application potential of the zinc sulfide in the aspect of photo-catalytic hydrogen production is reduced. In order to reduce the band gap of zinc sulfide and improve the visible light catalytic hydrogen production efficiency, methods such as metal ion doping, cation exchange, heterostructure growth and the like are introduced and the photocatalytic hydrogen production performance of the material is effectively improved, but few reports exist on a method for reducing the band gap by directly converting zinc sulfide into a porous zinc selenide nano material by utilizing anion exchange reaction.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing a zinc selenide ultrathin nanobelt by an anion exchange method, prepares a corresponding zinc selenide/molybdenum disulfide heterogeneous nanobelt by taking the zinc selenide/molybdenum disulfide ultrathin nanobelt as a precursor, and explores the application potential of the nanobelts in the aspect of photocatalysis. To this end, the present invention provides the following aspects:
a porous zinc selenide ultrathin nanobelt exhibiting an ultrathin band-like structure having a length of 5 to 10 μm, a width of 17 to 19nm and a thickness of less than 5nm, and the surface of the ultrathin nanobelt having a distinct porous structure.
A method for preparing the porous zinc selenide ultrathin nanobelt of <1>, wherein the method is performed using an anion exchange method, and the method comprises:
the first step is as follows: adding a proper amount of ultrathin zinc sulfide/diethylenetriamine hybrid nanobelt into an ultrasonic container, adding a proper amount of deionized water, and performing ultrasonic treatment and oscillation until the mixture is completely dissolved;
the second step is as follows: adding a proper amount of sodium selenite and hydrazine hydrate into the mixed solution, performing ultrasonic treatment and oscillation until the sodium selenite and the hydrazine hydrate are dissolved, transferring the solution into a corrosion-resistant reaction kettle, adding deionized water so that the total volume of the solution is 60-80% of the total volume of the reaction kettle, and reacting for 6-24 hours at 190 ℃ under 170-;
the third step: and centrifugally washing and freeze-drying the obtained dispersion liquid to obtain the zinc selenide ultrathin nanobelt.
<3> the method according to <2>, wherein
The zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt used in the first step is prepared by a method comprising the following steps:
step S1: putting a certain amount of zinc nitrate salt and dried diethylenetriamine into a container;
step S2: strong stirring and ultrasonic dissolving are alternately carried out until the zinc nitrate salt is dissolved;
step S3: adding equal molar amount of thiourea into the mixture, stirring, and performing ultrasonic treatment until the thiourea is dissolved;
step S4: transferring the resulting dispersion to a vessel and attaching an air condenser tube to the vessel;
step S5: heating at the temperature of 180 ℃ and 220 ℃ for reaction for 3-5h, stopping the reaction, and then cooling to room temperature;
step S6: filtering and washing with deionized water; and
step S7: the zinc sulfide (diethylenetriamine) ultrathin hybrid nano-belt can be obtained by freeze drying at the temperature of between 50 ℃ below zero and 80 ℃ below zero.
The method according to claim 3, wherein the zinc nitrate salt used in step S1 is zinc nitrate hexahydrate in an amount of 1 to 3mmol, the diethylenetriamine in step S1 is in an amount of 60 to 100ml, and the molar amount of thiourea added and the molar amount of zinc nitrate hexahydrate in step S3 are 1 to 3mmol, respectively.
The method for preparing an ultrathin zinc selenide nanobelt according to claim 2, wherein the molar content of the ultrathin zinc sulfide/diethylenetriamine hybrid nanobelt in the first step is 0.1-0.3mmol, and the volume of water is 10-15 ml.
The method for preparing an ultrathin zinc selenide nanobelt according to claim 2, wherein the molar content of sodium selenite in the second step is 1.75-3 times that of the ultrathin zinc selenide/diethylenetriamine hybrid nanobelt, and the added volume of hydrazine hydrate is 3-10 ml.
A zinc selenide/molybdenum disulfide hetero-nanobelt exhibiting a nanobelt-like structure having a length of 5 to 10 μm and a width of 17 to 19nm, and having a surface with a distinct porous structure, and a molybdenum disulfide hetero-node structure existing on the surface of the nanobelt.
A method of preparing the zinc selenide/molybdenum disulfide heterogeneous nanobelt of claim <7>, the method comprising:
step A1: adding the zinc selenide ultrathin nanobelt into a container for ultrasound, adding a proper amount of N, N-dimethylformamide, and performing ultrasound and oscillation until the zinc selenide ultrathin nanobelt is completely dissolved;
step A2: adding a proper amount of ammonium thiomolybdate and hydrazine hydrate into the mixed solution, performing ultrasonic treatment and oscillation until the ammonium thiomolybdate and the hydrazine hydrate are dissolved, continuously adding N, N-dimethylformamide so that the concentration of the ammonium thiomolybdate is in the range of 0.1-0.5mg/ml, transferring the ammonium thiomolybdate to a reaction kettle, wherein the total volume of the solution accounts for 60-80% of the volume of the reaction kettle, and reacting for 8-24h at 190 ℃ under 170-;
step A3: and centrifugally washing the obtained dispersion liquid, and freeze-drying at the temperature of between 50 ℃ below zero and 80 ℃ below zero to obtain the zinc selenide ultrathin nano-belt zinc selenide/molybdenum disulfide heterogeneous nano-belt.
The method for preparing zinc selenide/molybdenum disulfide heterogeneous nanobelts according to claim <8>, wherein the ratio of the zinc selenide ultra-thin nanobelts to the N, N-dimethylformamide added in the step a1 is 2-3ml of N, N-dimethylformamide added per 10mg of zinc selenide ultra-thin nanobelts.
The method for preparing a zinc selenide/molybdenum disulfide heterogeneous nanobelt according to claim <8>, wherein the ammonium thiomolybdate and hydrazine hydrate are added in an amount of 0.005-0.1ml of hydrazine hydrate per mg of ammonium thiomolybdate in step a 2.
According to the invention, the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt prepared in the patent application filed by the applicant on the same day is used as a precursor, the zinc selenide ultrathin nanobelt is obtained through a simple anion exchange reaction, and the zinc selenide/molybdenum disulfide heterogeneous nanobelt is further prepared through in-situ growth, and the obtained zinc selenide/molybdenum disulfide heterogeneous nanobelt has excellent hydrogen production performance by light, so that the zinc selenide/molybdenum disulfide hybrid ultrathin nanobelt has great application potential and application value in the aspect of photocatalysis.
Drawings
FIG. 1 is a scanning electron microscope photograph of the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt of the present invention;
FIG. 2 is a transmission electron microscope photograph of the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt of the present invention;
FIG. 3 is an atomic force microscope photograph of the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt of the present invention;
FIG. 4 is a powder X-ray diffraction image of the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt of the present invention;
FIG. 5 is a transmission electron microscope photograph of an ultrathin nanoribbon of porous zinc selenide of the present invention;
FIG. 6 is a powder X-ray diffraction image of the porous zinc selenide ultrathin nanoribbons of the invention;
FIG. 7 is a photograph of a transmission electron microscope of zinc selenide/molybdenum disulfide heterogeneous nanoribbons of the present invention;
FIG. 8 is a high resolution TEM image of ZnSe/ZnS heteronanoribbons of the present invention;
fig. 9 is a photo-hydrogen production performance picture of zinc selenide/molybdenum disulfide heterogeneous nanobelts of the present invention.
The obtained products were characterized by Zesiss Supra 40 Scanning Electron Microscope (SEM), JEOL-2010 Transmission Electron Microscope (TEM), Veeco DI Nano-scope multiMode V-type Atomic Force Microscope (AFM), Philips X' Pert PROSUPER type X-ray diffractometer (XRD), and the like, respectively.
Detailed Description
1) One aspect of the invention is to provide a zinc selenide ultrathin nanobelt prepared by an anion exchange method and a preparation method thereof.
The metal sulfide/amine hybrid nano material belongs to a novel and unique nano material, and has unique properties and rich and colorful nano structures, and the introduction of amine molecules can not only adjust the performance of the nano material, but also guide the crystal growth process of the nano material. Based on the unique properties and various nanostructures of the metal sulfide/amine hybrid nanomaterial, the metal sulfide/amine hybrid nanomaterial can be used as a good precursor to further prepare functional nanomaterials and devices. Therefore, on the basis of the application of 'a zinc sulfide/diethylenetriamine hybrid and zinc sulfide ultrathin nanobelt and a preparation method thereof' filed on the same day, the inventor tries to prepare the multi-element hybrid nanomaterial by anion exchange so as to further improve the performance and widen the application prospect.
The porous zinc selenide ultrathin nanobelt provided by the invention has an ultrathin strip-shaped structure with the length of 5-10 mu m, the width of 17-19nm and the thickness of less than 5nm, and the surface of the ultrathin nanobelt has an obvious porous structure. The term "substantially porous structure" means a porous structure that can be easily judged by one of ordinary skill in the art to be at least 50% or more, even 60% or more, 70% or more, 80% or more, or 85% or more, porous.
The "band" in the ultrathin nanobelt of zinc selenide described in the present invention refers to a structure of: the elongated strips, i.e., the lengths and widths are significantly different, with the lengths being significantly or much greater than the widths.
In the present invention, the zinc sulfide/diethylenetriamine hybrid nanobelt material used as a raw material is prepared by the inventors of the present application, but the applicant expects that the raw material used in the present invention should not be limited thereto, and that commercially available or otherwise obtained zinc sulfide/diethylenetriamine hybrid nanobelt material should also be used as time goes by and the related research work in the art progresses.
The invention provides a method for preparing a porous zinc selenide ultrathin nanobelt, wherein the method is carried out by adopting an anion exchange method and comprises the following steps:
the first step is as follows: adding a proper amount of ultrathin zinc sulfide/diethylenetriamine hybrid nanobelt into an ultrasonic container, adding a proper amount of deionized water, and performing ultrasonic treatment and oscillation until the mixture is completely dissolved;
the second step is as follows: adding a proper amount of sodium selenite and hydrazine hydrate into the mixed solution, performing ultrasonic treatment and oscillation until the sodium selenite and the hydrazine hydrate are dissolved, adding deionized water to ensure that the volume of the solution accounts for 60-80% of the total volume of the reaction kettle, then transferring the solution to a corrosion-resistant reaction kettle, and reacting for 6-24 hours at the temperature of 190 ℃;
the third step: and centrifugally washing the obtained dispersion liquid, and freeze-drying at the temperature of between 50 ℃ below zero and 80 ℃ below zero to obtain the zinc selenide ultrathin nanobelt.
In one specific embodiment of the present invention for preparing the porous zinc selenide ultrathin nanobelt, the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt used in the first step is prepared by a method comprising the steps of:
step S1: putting a certain amount of zinc nitrate salt and dried diethylenetriamine into a container;
step S2: strong stirring and ultrasonic dissolving are alternately carried out until the zinc nitrate salt is dissolved;
step S3: adding equal molar amount of thiourea into the mixture, stirring, and performing ultrasonic treatment until the thiourea is dissolved;
step S4: transferring the resulting dispersion to a vessel and attaching an air condenser tube to the vessel;
step S5: heating at the temperature of 180 ℃ and 220 ℃ for reaction for 3-5h, stopping the reaction, and then cooling to room temperature;
step S6: filtering and washing with deionized water; and
step S7: the zinc sulfide (diethylenetriamine) ultrathin hybrid nano-belt can be obtained by freeze drying at the temperature of between 50 ℃ below zero and 80 ℃ below zero.
In a more specific embodiment of the present invention, the method for preparing the zinc sulfide ultrathin nanobelt comprises the following specific steps:
step S1: charging: certain Zn (NO)3)2·6H2Filling O and pure diethylenetriamine into a container;
step S2: dissolving: strong stirring and ultrasonic dissolving are alternately carried out until the zinc salt is dissolved.
Step S3: charging: adding appropriate amount of thiourea into the mixture, stirring, and dissolving with ultrasound.
Step S4: transferring: the resulting dispersion was transferred to a round bottom flask and connected to an air condenser.
Step S5: heating: the reaction was heated in an oil bath and then cooled to room temperature in air.
Step S6: and (3) filtering: the resulting dispersion was filtered with filter paper and purified with deionized water.
Step S7: and (3) drying: the final product was obtained by vacuum freeze drying.
Step S8: heating and reacting: heated in a tube furnace and reacted in a nitrogen atmosphere.
Further, in a more specific embodiment, the zinc nitrate salt used in the above step S1 is zinc nitrate hexahydrate in an amount of 1 to 3mmol, the diethylenetriamine in the above step S1 is in an amount of 60 to 100ml, and the molar amount of thiourea added and the amount of zinc nitrate hexahydrate in the above step S3 are 1 to 3mmol, respectively.
In the reaction for synthesizing the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt, pure dry diethylenetriamine (for example, the water content is below 0.1 mass%) is adopted as the solvent, while a diethylenetriamine/water mixed solvent is not adopted, and under the condition of not being bound by any theory, the inventor speculates that the dissociation of zinc salt and diethylenetriamine is promoted by the presence of water, namely, divalent zinc ions and diethylenetriamine with one positive charge are formed (the diethylenetriamine is expressed by DETA, and the diethylenetriamine with one positive charge is DETA)+) And correspondingly generate hydroxyl monovalent negative ions, the existence of the hydroxyl can promote divalent zinc ions to form two-dimensional layered Zn (OH)2-x(NO3)x mH2O (length and width approach) composite precursor template, and Zn (OH)2-x(NO3)x mH2The O composite material precursor template can be used as a two-dimensional lamellar template for the alternate growth of zinc sulfide-diethylenetriamine, and finally, a two-dimensional flaky zinc sulfide-diethylenetriamine hybrid nanosheet is generated, but the two-dimensional flaky zinc sulfide-diethylenetriamine hybrid nanosheet cannot form two-dimensional Zn (OH) under an anhydrous environment2-x(NO3)x mH2O, corresponding to twoDirect neutralization of-NH in zinc-valent acid with diethylenetriamine2The groups form a ligand, and the two sides of the diethylenetriamine molecule are respectively provided with an-NH2The radicals divalent zinc and-NH, respectively2And (3) coordinating the groups to generate zinc sulfide, further growing the zinc sulfide/diethylenetriamine hybrid nano material along the direction vertical to the molecular chain of diethylenetriamine, and finally generating the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt.
The zinc sulfide/diethylenetriamine ultrathin nanobelt obtained by the invention belongs to the field of zinc sulfide/diethylenetriamine hybrid nanobelts and is synthesized for the first time. A specific example thereof is zinc sulfide (diethylenetriamine)0.5Ultra-thin hybrid nanobelts.
In the present invention, an air condensation duct having a length of 30-60cm is used to reduce rapid evaporation of moisture.
For example, in one embodiment of the present invention for preparing ultrathin nanoribbons of zinc selenide, the process of the present invention comprises:
the first step is as follows: weighing a proper amount of ultrathin zinc sulfide/diethylenetriamine hybrid nanobelt, adding the mixture into a 50ml centrifugal tube, adding a proper amount of deionized water, and performing ultrasonic treatment and oscillation until the mixture is completely dissolved;
the second step is as follows: adding a proper amount of sodium selenite and hydrazine hydrate into the mixed solution, performing ultrasonic treatment and oscillation until the sodium selenite and the hydrazine hydrate are dissolved, adding water to 30-40ml, transferring the solution to a 50ml polytetrafluoroethylene reaction kettle, and reacting for 6-24h at the temperature of 190 ℃;
the third step: and centrifugally washing and freeze-drying the obtained dispersion liquid to obtain the zinc selenide ultrathin nanobelt.
In another embodiment of the present invention for preparing the zinc selenide ultrathin nanobelt, the molar content of the ultrathin zinc sulfide/diethylenetriamine hybrid nanobelt used in the first step is 0.1-0.3mmol, and the volume of water is 10-15 ml.
In another embodiment of the present invention for preparing the ultrathin zinc selenide nanobelt, the molar content of sodium selenite in the second step is 1.75-3 times that of the ultrathin zinc selenide/diethylenetriamine hybrid nanobelt, and the addition volume of hydrazine hydrate of 85% is 3-10 ml.
2) The invention provides a zinc selenide/molybdenum disulfide heterogeneous nano-belt and a preparation method thereof.
The zinc selenide/molybdenum disulfide heterogeneous nanobelt of the invention has a nanobelt-shaped structure with the length of 5-10 μm and the width of 17-19nm, the surface of the ultrathin nanobelt has an obvious pore structure, and a molybdenum disulfide heterojunction structure exists on the surface of the nanobelt.
The method for preparing the zinc selenide/molybdenum disulfide heterogeneous nanobelt comprises the following steps:
step A1: adding the zinc selenide ultrathin nanobelt into a container for ultrasound, adding a proper amount of N, N-dimethylformamide, and performing ultrasound and oscillation until the zinc selenide ultrathin nanobelt is completely dissolved;
step A2: adding a proper amount of ammonium thiomolybdate and hydrazine hydrate into the mixed solution, performing ultrasonic treatment and oscillation until the ammonium thiomolybdate and the hydrazine hydrate are dissolved, continuously adding N, N-dimethylformamide so that the concentration of the ammonium thiomolybdate is in a range, transferring the ammonium thiomolybdate to a polytetrafluoroethylene reaction kettle, and reacting for 8-24 hours at the temperature of 190 ℃;
step A3: and centrifugally washing the obtained dispersion liquid, and freeze-drying at the temperature of between 50 ℃ below zero and 80 ℃ below zero to obtain the zinc selenide ultrathin nano-belt zinc selenide/molybdenum disulfide heterogeneous nano-belt.
In a specific embodiment of the invention, the method for preparing the zinc selenide/molybdenum disulfide heterogeneous nanobelt by using the zinc selenide ultrathin nanobelt as the precursor comprises the following steps:
step A1: weighing a proper amount of zinc selenide ultrathin nanobelts, adding the zinc selenide ultrathin nanobelts into a 50ml centrifugal tube, adding a proper amount of N, N-dimethylformamide, and performing ultrasonic treatment and oscillation until the zinc selenide ultrathin nanobelts are completely dissolved;
step A2: adding a proper amount of ammonium thiomolybdate and hydrazine hydrate into the mixed solution, performing ultrasonic treatment and vibration until the ammonium thiomolybdate and the hydrazine hydrate are dissolved, continuously adding N, N-dimethylformamide to 30-40ml, transferring the mixture to a 50ml polytetrafluoroethylene reaction kettle, and reacting for 8-24h at 190 ℃ under 170-;
step A3: and centrifugally washing and freeze-drying the obtained dispersion liquid to obtain the zinc selenide ultrathin nano-belt zinc selenide/molybdenum disulfide heterogeneous nano-belt.
In another embodiment of the present invention for preparing zinc selenide/molybdenum disulfide heterogeneous nanobelts, the mass of the zinc selenide ultrathin nanobelt in the step a1 is 10-50mg, and the volume of N, N-dimethylformamide is 10-15 ml.
In another embodiment of the present invention for preparing the zinc selenide/molybdenum disulfide heterogeneous nanobelt, the ammonium thiomolybdate and 85 mass% hydrazine hydrate added in the step a2 are respectively 3-10mg and 0.03-0.30 ml.
According to SEM, TEM and AFM photographs, the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt obtained by the invention has a uniform appearance, and has the specific length of 5-10 μm, the thickness of about 3-5nm (the average value is 4nm) and the width of 17-19nm (the average value is 18 nm). The corresponding XRD pattern further confirms the zinc sulfide/diethylenetriamine hybrid nanostructure (which is consistent with Advanced Materials, 2002, 14, 296-300, Small, 2005, 1, 320-325). The zinc selenide ultra-thin nanobelt prepared by the transmission electron microscope can maintain the original ultra-thin belt-shaped structure, the surface has rich pores, the photocatalytic active area of the material is further increased, specifically, the length is still maintained at 5-10 mu m, the width is 17-19nm (the average value is 18nm), the contrast of the obtained zinc selenide nanobelt is very shallow and is close to transparency through the transmission electron microscope, the ultra-thin thickness of the zinc selenide nanobelt is proved, in addition, the zinc selenide nanobelt obtained by the transmission can be known to have good water solubility and dispersibility, the zinc selenide/molybdenum disulfide heterogeneous nanobelt prepared by further growing molybdenum disulfide on the basis keeps the original belt-shaped structure, and the obvious molybdenum disulfide heterogeneous knot structure is found on the surface of the nanobelt at high resolution, the material still has good water dispersibility, further photohydrogen production tests show that zinc selenide has good photohydrogen production catalytic activity, and heterostructure molybdenum disulfide further remarkably improves the photocatalytic performance, so that the huge application potential and application value of the material in photocatalysis are further demonstrated.
Examples
The technical solution of the present invention is further described below with reference to the accompanying drawings, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Example 1
Preparation of zinc sulfide/diethylenetriamine hybrid nanobelt
To a 250ml beaker was added 1mmol of Zn (NO)3)2·6H2Adding 75ml of fresh and dry diethylenetriamine, strongly stirring and ultrasonically treating to dissolve the zinc salt; then adding 1mmol of thiourea into the mixed solution, and carrying out ultrasonic treatment and stirring to dissolve the thiourea; transferring the obtained dispersion to a 125ml single-neck flask and connecting the single-neck flask to a 35cm air condenser tube, heating the mixture in an oil bath at 220 ℃ for reaction for 3 hours, and naturally cooling the mixture to room temperature; further filtering and washing by using filter paper and freeze-drying at about-70 ℃ to obtain the zinc sulfide/diethylenetriamine hybrid ultrathin nanobelt.
Preparation of porous zinc selenide ultrathin nanobelt
Weighing 19.5mg of ultrathin zinc sulfide/diethylenetriamine hybrid nanobelt, adding the mixture into a 50ml centrifugal tube, adding 15ml of deionized water, performing ultrasonic vibration until the mixture is completely dissolved, then adding 69.2mg of sodium selenite and 5ml of hydrazine hydrate into the mixture, performing ultrasonic vibration until the mixture is dissolved, adding water to 35ml, transferring the mixture to a 50ml polytetrafluoroethylene reaction kettle, reacting for 12 hours at 180 ℃, finally performing centrifugal washing on the obtained dispersion system, and performing freeze drying at about-70 ℃ to obtain the porous ultrathin zinc selenide nanobelt.
Example 2:
the difference between the embodiment and the specific example 1 is that the mass of the ultrathin zinc sulfide/diethylenetriamine hybrid nano-belt is changed to 26mg, then the volume of deionized water is 10ml, the volume of hydrazine hydrate is 8ml, and the reaction temperature is changed to 185 ℃.
Example 3:
the embodiment is different from the specific embodiment 1 in that the amounts of the zinc selenide ultrathin nanobelt, the N, N-dimethylformamide and the hydrazine hydrate are respectively changed to 15mg, 12ml and 0.10ml, the reaction temperature is changed to 175 ℃, and the reaction is carried out for 15 hours.
Example 4
Further, the zinc selenide ultrathin nanobelt obtained in the above example 1 is used as a precursor to prepare a zinc selenide/molybdenum disulfide heterogeneous nanobelt:
weighing 20mg of porous zinc selenide ultrathin nanobelt, adding the porous zinc selenide ultrathin nanobelt into a 50ml centrifugal tube, adding 15ml of N, N-dimethylformamide, carrying out ultrasonic treatment and oscillation until the mixture is completely dissolved, then adding 5mg of ammonium thiomolybdate and 0.05ml of hydrazine hydrate into the mixed solution, further carrying out ultrasonic treatment and oscillation until the mixture is dissolved, continuously adding the N, N-dimethylformamide to 35ml, transferring the mixture to a 50ml polytetrafluoroethylene reaction kettle, reacting for 12 hours at 180 ℃, and finally carrying out centrifugal washing and freeze drying on the obtained dispersion liquid to obtain the zinc selenide/molybdenum disulfide heterogeneous nanobelt.
Example 5
This embodiment is different from example 4 in that the amounts of ammonium thiomolybdate and hydrazine hydrate were changed to 10mg and 0.8ml, respectively.
Example 6
This embodiment is different from example 4 in that the reaction temperature was changed to 190 ℃.
Industrial applicability
The zinc selenide nanobelt prepared by the invention has good water solubility and dispersibility and good photocatalytic activity for hydrogen production by light, and the prepared molybdenum disulfide with a heterostructure further remarkably improves the photocatalytic performance. The materials are expected to have huge application potential and application value in the aspect of photocatalysis.
Claims (10)
1. A porous ultrathin zinc selenide nanoribbon exhibiting an ultrathin ribbon-like structure of 5-10 μm in length, 17-19nm in width and less than 5nm in thickness, the surface of the ultrathin nanoribbon having an apparent porous structure, and the powder X-ray diffraction of the porous ultrathin zinc selenide nanoribbon exhibiting a wurtzite phase.
2. A method of making the porous ultrathin zinc selenide nanoribbons of claim 1, wherein the method is performed using an anion exchange process and does not require the use of an annealing process, and comprises:
the first step is as follows: adding a proper amount of ultrathin zinc sulfide/diethylenetriamine hybrid nanobelt into an ultrasonic container, adding a proper amount of deionized water, and performing ultrasonic treatment and oscillation until the mixture is completely dissolved;
the second step is as follows: adding a proper amount of sodium selenite and hydrazine hydrate into the mixed solution, performing ultrasonic treatment and oscillation until the sodium selenite and the hydrazine hydrate are dissolved, transferring the solution into a corrosion-resistant reaction kettle, adding deionized water so that the total volume of the solution is 60-80% of the total volume of the reaction kettle, and reacting for 6-24 hours at 190 ℃ under 170-;
the third step: and centrifugally washing and freeze-drying the obtained dispersion liquid to obtain the zinc selenide ultrathin nanobelt.
3. The method of claim 2, wherein
The zinc sulfide/diethylenetriamine hybrid ultrathin nanometer band adopted in the first step is prepared by a method comprising the following steps:
step S1: putting a certain amount of zinc nitrate salt and dried diethylenetriamine into a container;
step S2: strong stirring and ultrasonic dissolving are alternately carried out until the zinc nitrate salt is dissolved;
step S3: adding equal molar amount of thiourea into the mixture, stirring, and performing ultrasonic treatment until the thiourea is dissolved;
step S4: transferring the resulting dispersion to a vessel and attaching an air condenser tube to the vessel;
step S5: heating at the temperature of 180 ℃ and 220 ℃ for reaction for 3-5h, stopping the reaction, and then cooling to room temperature;
step S6: filtering and washing with deionized water; and
step S7: the zinc sulfide (diethylenetriamine) ultrathin hybrid nano-belt can be obtained by freeze drying at the temperature of between 50 ℃ below zero and 80 ℃ below zero.
4. The method according to claim 3, wherein the zinc nitrate salt used in step S1 is zinc nitrate hexahydrate in an amount of 1-3mmol, the diethylenetriamine in step S1 is in an amount of 60-100ml, and the molar amount of thiourea added in step S3 is 1-3mmol, respectively, as zinc nitrate hexahydrate.
5. The method for preparing ultrathin zinc selenide nanobelts according to claim 2, wherein the molar content of the ultrathin zinc sulfide/diethylenetriamine hybrid nanobelt in the step S1 is 0.1-0.3mmol, and the volume of water is 10-15 ml.
6. The method for preparing an ultrathin zinc selenide nanobelt according to claim 2, wherein the molar content of sodium selenite in step S2 is 1.75-3 times that of the ultrathin zinc selenide/diethylenetriamine hybrid nanobelt, and the added volume of hydrazine hydrate is 3-10 ml.
7. A zinc selenide/molybdenum disulfide hetero-nanobelt exhibiting a nanobelt-like structure of 5-10 μm in length and 17-19nm in width, and having a distinct porous structure on the surface thereof, and a molybdenum disulfide hetero-node structure on the surface thereof.
8. A method of making the zinc selenide/molybdenum disulfide heterogeneous nanoribbon of claim 7, the method comprising:
step A1: adding the zinc selenide ultrathin nanobelt according to claim 1 or the zinc selenide ultrathin nanobelt prepared by the method of any one of claims 2 to 6 into a container for ultrasound, adding a proper amount of N, N-dimethylformamide, and performing ultrasound and oscillation until the zinc selenide ultrathin nanobelt is completely dissolved;
step A2: adding a proper amount of ammonium thiomolybdate and hydrazine hydrate into the mixed solution, performing ultrasonic treatment and oscillation until the ammonium thiomolybdate and the hydrazine hydrate are dissolved, continuously adding N, N-dimethylformamide so that the concentration of the ammonium thiomolybdate is in the range of 0.1-0.5mg/ml, transferring the ammonium thiomolybdate to a reaction kettle, wherein the total volume of the solution accounts for 60-80% of the volume of the reaction kettle, and reacting for 8-24h at 190 ℃ under 170-;
step A3: and centrifugally washing the obtained dispersion liquid, and freeze-drying at the temperature of between 50 ℃ below zero and 80 ℃ below zero to obtain the zinc selenide ultrathin nano-belt zinc selenide/molybdenum disulfide heterogeneous nano-belt.
9. The method for preparing zinc selenide/molybdenum disulfide heterogeneous nanobelts according to claim 8, wherein the ratio of the zinc selenide ultrathin nanobelts to the N, N-dimethylformamide added in step a1 is 2-3ml of N, N-dimethylformamide added per 10mg of zinc selenide ultrathin nanobelts.
10. The method for preparing zinc selenide/molybdenum disulfide heterogeneous nanobelts according to claim 8, wherein the amount of ammonium thiomolybdate and hydrazine hydrate added in step A2 is 0.005-0.1ml of hydrazine hydrate per mg of ammonium thiomolybdate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710668586.2A CN107572489B (en) | 2017-08-07 | 2017-08-07 | Zinc selenide ultrathin nanobelt and anion exchange method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710668586.2A CN107572489B (en) | 2017-08-07 | 2017-08-07 | Zinc selenide ultrathin nanobelt and anion exchange method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107572489A CN107572489A (en) | 2018-01-12 |
| CN107572489B true CN107572489B (en) | 2020-01-03 |
Family
ID=61035362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710668586.2A Active CN107572489B (en) | 2017-08-07 | 2017-08-07 | Zinc selenide ultrathin nanobelt and anion exchange method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107572489B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110562935B (en) * | 2019-09-20 | 2022-11-08 | 安徽大学 | Strip-shaped frame-shaped ZnSe nano material, preparation method thereof and application thereof in colorimetric detection of heavy metal ions |
| CN111573632B (en) * | 2020-05-27 | 2023-05-12 | 安徽大学 | Ribbon PbSe/ZnSe heterojunction nano material and preparation method and application thereof |
| CN116273073A (en) * | 2023-01-10 | 2023-06-23 | 常州大学 | ZnSe/ZnCo 2 S 4 Composite material and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040201A (en) * | 2010-11-05 | 2011-05-04 | 新疆大学 | Solvothermal controllable method for preparing ZnSe and ZnTe nano materials |
| CN103159189A (en) * | 2013-04-03 | 2013-06-19 | 南京理工大学 | Synthesis method of ZnSe hollow microspheres by alcohol thermal reduction |
| CN103641169A (en) * | 2013-11-12 | 2014-03-19 | 江苏大学 | Synthetic method of Bi2S3-MoS2 nanometer heterostructure |
| CN106011521A (en) * | 2016-07-15 | 2016-10-12 | 江苏大学 | Copper-based electric contact material containing graphene/molybdenum disulfide heterojunctions and preparation method of copper-based electric contact material |
-
2017
- 2017-08-07 CN CN201710668586.2A patent/CN107572489B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040201A (en) * | 2010-11-05 | 2011-05-04 | 新疆大学 | Solvothermal controllable method for preparing ZnSe and ZnTe nano materials |
| CN103159189A (en) * | 2013-04-03 | 2013-06-19 | 南京理工大学 | Synthesis method of ZnSe hollow microspheres by alcohol thermal reduction |
| CN103641169A (en) * | 2013-11-12 | 2014-03-19 | 江苏大学 | Synthetic method of Bi2S3-MoS2 nanometer heterostructure |
| CN106011521A (en) * | 2016-07-15 | 2016-10-12 | 江苏大学 | Copper-based electric contact material containing graphene/molybdenum disulfide heterojunctions and preparation method of copper-based electric contact material |
Non-Patent Citations (2)
| Title |
|---|
| Large-Scale Syntheses of Zinc Sulfide•(Diethylenetriamine)0.5 Hybrids as Precursors for Sulfur Nanocomposite Cathodes;Tao Ma等;《Angew. Chem. Int. Ed.》;20170804;第11836 –11840页 * |
| Nanocrystals of an Inorganic–Organic Hybrid Semiconductor: Formation of Uniform Nanobelts of [ZnSe](Diethylenetriamine)0.5 in a Ternary Solution;Weitang Yao等;《Adv. Mater.》;20051011;第2799–2802页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107572489A (en) | 2018-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Rational synthesis of MnxCd1-xS for enhanced photocatalytic H2 evolution: Effects of S precursors and the feed ratio of Mn/Cd on its structure and performance | |
| Yu et al. | General synthesis of single‐crystal tungstate nanorods/nanowires: a facile, low‐temperature solution approach | |
| Xie et al. | Morphological control in solvothermal synthesis of titanium oxide | |
| CN102259907B (en) | Porous zinc oxide nano material and preparation method thereof | |
| CN107572489B (en) | Zinc selenide ultrathin nanobelt and anion exchange method for preparing same | |
| Jia et al. | Microwave-assisted synthesis of anatase TiO2 nanorods with mesopores | |
| Panigrahi et al. | The growth of bismuth sulfide nanorods from spherical-shaped amorphous precursor particles under hydrothermal condition | |
| Chen et al. | Controlled synthesis of high crystalline bismuth sulfide nanorods: using bismuth citrate as a precursor | |
| CN108246331B (en) | ZnS micron composite material modified by graphene nitrogen carbide quantum dots and preparation method and application thereof | |
| Fan et al. | Colloidal nanocrystals of orthorhombic Cu 2 ZnGeS 4: phase-controlled synthesis, formation mechanism and photocatalytic behavior | |
| Gao et al. | Solution–solid growth of α-monoclinic selenium nanowires at room temperature | |
| Cui et al. | Large scale selective synthesis of α-Co (OH) 2 and β-Co (OH) 2 nanosheets through a fluoride ions mediated phase transformation process | |
| Fan et al. | Colloidal synthesis and photocatalytic properties of orthorhombic AgGaS 2 nanocrystals | |
| Zhuang et al. | Two‐dimensional transition metal oxides and chalcogenides for advanced photocatalysis: progress, challenges, and opportunities | |
| CN107572581A (en) | The preparation method of metal sulfide/amine hybrid nano-material and nano metal sulfide material | |
| CN104192914B (en) | A kind of preparation method of manganese tungstate monocrystal nanowire | |
| Zahmatkeshani et al. | Synthesis of SnO 2, Zn-doped SnO 2 and Zn 2 SnO 4 nanostructure-based hierarchical architectures by using deep eutectic precursors and their photocatalytic application | |
| CN111530459A (en) | Preparation method and application of 0D/2D composite material based on AlOOH nanosheets | |
| Yan et al. | A solution-phase approach to the chemical synthesis of ZnO nanostructures via a low-temperature route | |
| Yang et al. | Molten Salt-Mediated Surface Reconstruction Induced Orientation-Growth of 1D/2D Heterostructure for High-Sensitivity H2S Gas Sensing | |
| CN1298632C (en) | Prepn process of nano copper iodide powder | |
| CN109399692B (en) | Preparation method of self-assembled hexagonal prism zinc oxide | |
| CN101941677A (en) | Method for preparing manganese oxide surface modified zinc oxide nano rod | |
| Wang et al. | Zinc Sulfide Nanosheet-Based Hybrid Superlattices with Tunable Architectures Showing Enhanced Photoelectrochemical Properties. | |
| Yuan et al. | Rod-like Co 2 P nanostructures: improved synthesis, catalytic property and application in the removal of heavy metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |