CN109317167B - Metal chalcogenide complex coated nano particle and preparation method and application thereof - Google Patents

Metal chalcogenide complex coated nano particle and preparation method and application thereof Download PDF

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CN109317167B
CN109317167B CN201811277502.3A CN201811277502A CN109317167B CN 109317167 B CN109317167 B CN 109317167B CN 201811277502 A CN201811277502 A CN 201811277502A CN 109317167 B CN109317167 B CN 109317167B
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CN109317167A (en
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孙海珠
王立晶
陈楠楠
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Northeast Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J35/33—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices

Abstract

The invention provides a metal chalcogenide complex coated nano particle and a preparation method and application thereof, belonging to a preparation method of a multi-element semiconductor nano material. Firstly, dropwise adding sulfide solution into tin salt solution to obtain Sn2S7 6‑An MCC ligand; adding concentrated ammonia water into a transition metal salt solution to obtain a transition metal complex; dropwise adding the transition metal complex into the ligand, and stirring to obtain the MCC-Cu2MSn2S7(M ═ Zn, Co, Ni) nanoparticles; the nanoparticles are subjected to anti-precipitation purification by isopropanol to obtain Cu coated by the metal chalcogenide complex2MSn2S7Nanoparticles. The nano particles prepared by the method not only have good electrochemical hydrogen production performance, but also have strong photovoltaic response capability, and can be applied to the photoelectric fields of electro-catalytic hydrogen production, water-phase nanocrystalline batteries and the like.

Description

Metal chalcogenide complex coated nano particle and preparation method and application thereof
Technical Field
The invention belongs to a preparation method of a multi-element semiconductor nano material, and particularly relates to a metal chalcogenide complex coated nano particle, and a preparation method and application thereof.
Background
Cu2MSn2S7The (M ═ Zn, Co and Ni) nanoparticles have the advantages of low toxicity, low consumption, high stability and abundant raw materials, and are widely applied to the photoelectric field. Compared with nanoparticles coated with organic ligands, metal chalcogenides (MCCs) have many advantages as inorganic ligands, such as strong hydrophilicity, good conductivity, many active sites, etc. However, the existing MCC ligand coated Cu2MSn2S7The preparation method of the nano-particle is complex, and the Cu coated with the organic ligand is generally prepared first2MSn2S7Then ligand cross-linkingBy changing to MCC-Cu2MSn2S7The reaction process of the nano particles is complex and time-consuming, and high-toxicity organic solvents are needed, so that the preparation cost is high, and the industrial production is not facilitated. MCC-Cu obtained without ligand exchange method2MSn2S7The preparation period is too long, the purification difficulty is high, the solubility and the film-forming property are low, and the application in the fields of aqueous phase photovoltaic devices and the like is severely limited.
Disclosure of Invention
The purpose of the invention is to solve the existing Cu2MSn2S7The preparation method of the nano-particle is complex, high-toxicity organic solvent is used, the preparation period is long, and the solubility and the film-forming property are poor, so that the nano-particle coated by the metal chalcogenide complex, the preparation method and the application thereof are provided.
The invention provides a preparation method of a metal chalcogenide complex coated nano particle, which comprises the following steps:
the method comprises the following steps: dropwise adding the sulfide solution into the tin salt solution to obtain Sn2S7 6-An MCC ligand;
step two: adding concentrated ammonia water into a transition metal salt solution to obtain a transition metal complex; the transition metal salt solution is selected from copper salt and at least one of zinc salt, cobalt salt or nickel salt;
step three: dropwise adding the transition metal complex obtained in the step two into the ligand obtained in the step one, and stirring to obtain the MCC-Cu2MSn2S7Nanoparticles;
step four: the MCC-Cu obtained in the third step2MSn2S7The nano particles are subjected to anti-precipitation purification by isopropanol to obtain Cu coated by the metal chalcogenide complex2MSn2S7Nanoparticles.
Preferably, the volume ratio of the step monosulfide solution to the tin salt solution is 7: 2.
preferably, the sulfide is sodium sulfide or potassium sulfide, and the tin salt is tin chloride or tin bromide.
Preferably, the copper salt is copper chloride, copper acetate or copper sulfate; the zinc salt is zinc chloride, zinc acetate or zinc sulfate; the cobalt salt is cobalt chloride, cobalt acetate or cobalt sulfate; the nickel salt is nickel chloride, nickel acetate or nickel sulfate.
Preferably, the concentration of the concentrated ammonia water in the second step is 13mol/L, and the concentration of the transition metal salt solution is 0.125 mol/L.
Preferably, the MCC-Cu of step four2MSn2S7The volume ratio of the nanoparticles to the isopropanol is (1-3) to 1.
Preferably, the obtained MCC-Cu2MSn2S7After the nano particles, the MCC-Cu of the step three is also included2MSn2S7Heating the nano particles to obtain hollow annular MCC-Cu2MSn2S7Nanoparticles;
preferably, the heating temperature is 200 ℃ and the heating time is 10-30 minutes.
The invention also provides the metal chalcogenide complex coated nano particle obtained by the preparation method.
The invention also provides application of the metal chalcogenide complex-coated nano particles in the fields of aqueous phase inorganic nanocrystalline solar cells and electro-catalysis hydrogen production.
The invention has the advantages of
The invention provides a metal chalcogenide complex coated nano particle and a preparation method and application thereof2Encounter Na2S·9H2Nature of O to form complexes towards SnCl4·5H2Dropwise adding excessive Na into O solution2S·9H2O to obtain Sn2S7 6-Adding excessive ammonia water into the transition metal salt solution to form a transition metal complex according to the property that the transition metal cation is easy to coordinate with ammonia gas, and combining the transition metal complex with the MCC ligand by utilizing the stronger coordination capacity of the MCC ligand to form multi-element MCC-Cu2MSn2S7Nanoparticles and the bonding capability of each component of the multi-component compound is improved by short-time high-temperature heating to obtainHollow annular MCC-Cu with size of 20nm and good crystallinity2MSn2S7Finally, the nano particles are subjected to reverse precipitation in isopropanol by utilizing the characteristic that MCC ligand is easy to precipitate in isopropanol, impurity ions introduced in the reaction process can be removed after the isopropanol reverse precipitation treatment, and the MCC-Cu is greatly improved2MSn2S7Purity of nanoparticles to obtain MCC-Cu of high purity and solubility2MSn2S7And (3) solution.
In addition, the nano particles after reverse precipitation have higher solubility in water, and the solubility is as high as 100mg mL-1This ensures a higher film-forming property of the nanoparticles. MCC-Cu prepared by the invention2MSn2S7The nano particles not only have good electrochemical hydrogen production performance, but also have stronger photovoltaic response capability, and when MCC-Cu is used, the nano particles have higher electrochemical hydrogen production performance2ZnSn2S7When the nano particles are active layers, the preparation of the low-toxicity aqueous phase inorganic nanocrystalline solar cell can be really realized. Thus, the MCC-Cu of the present invention can be used2MSn2S7The nano particles are applied to the photoelectric fields of electro-catalysis hydrogen production, water-phase nanocrystalline batteries and the like.
Drawings
FIG. 1 shows MCC-Cu prepared in example 12ZnSn2S7(ii) the (a) IR and (b) Raman spectra of the nanoparticles;
FIG. 2 shows MCC-Cu prepared in example 12ZnSn2S7XRD spectroscopy of the nanoparticles;
FIG. 3 shows MCC-Cu prepared in example 12ZnSn2S7TEM photograph of the nanoparticles;
FIG. 4 shows MCC-Cu prepared in example 12ZnSn2S7EDX data for nanoparticles;
FIG. 5 shows MCC-Cu prepared in example 22NiSn2S7Nanoparticles and MCC-Cu prepared in example 32CoSn2S7XRD spectroscopy of the nanoparticles;
FIG. 6 shows MCC-Cu prepared in examples 1 to 32MSn2S7UV profile of the nanoparticles;
FIG. 7 is the MCC-Cu prepared in example 12ZnSn2S7XPS spectroscopy of the nanoparticles;
FIG. 8 is a hollow ring-shaped MCC-Cu prepared in example 52ZnSn2S7TEM photograph of the nanoparticles;
FIG. 9 shows MCC-Cu prepared in examples 1 to 52MSn2S7Linear voltammograms of the nanoparticles;
FIG. 10 is aqueous MCC-Cu prepared in example 62ZnSn2S7Current-voltage curves for NCs devices.
Detailed Description
The invention provides a preparation method of a metal chalcogenide complex coated nano particle, which comprises the following steps:
the method comprises the following steps: dropwise adding the sulfide solution into the tin salt solution to obtain Sn2S7 6-MCC ligands (MCC ligands are metal chalcogenides); the volume ratio of the tin salt solution to the tin salt solution is preferably 7: 2, the concentration of the tin salt solution is preferably 0.035mol/L, and the concentration of the tin salt solution is preferably 0.035 mol/L; the tin salt is preferably tin chloride or tin bromide, and the sulfide is preferably sodium sulfide or potassium sulfide;
step two: adding concentrated ammonia water into a transition metal salt solution to obtain a transition metal complex; the transition metal salt solution is selected from copper salt and at least one of zinc salt, cobalt salt or nickel salt; the copper salt is preferably copper chloride, copper acetate or copper sulfate; the zinc salt is preferably zinc chloride, zinc acetate or zinc sulfate; the cobalt salt is preferably cobalt chloride, cobalt acetate or cobalt sulfate; the nickel salt is preferably nickel chloride, nickel acetate or nickel sulfate; the concentration of the strong ammonia water is preferably 13mol/L, and the concentration of the transition metal salt solution is preferably 0.125 mol/L;
step three: dropwise adding the transition metal complex obtained in the step two into the ligand obtained in the step one, and stirring to obtain the MCC-Cu2MSn2S7Nanoparticles; the stirring time is preferably 10 to 60 minutes, and more preferably 30 minutes; the transition metal complexThe volume ratio of the compound to the ligand is preferably 1: 15; the transition metal complex is a copper-containing complex and at least one selected from a zinc-containing complex, a cobalt-containing complex and a nickel-containing complex; the volume ratio of the copper-containing complex to the zinc-containing complex, cobalt-containing complex or nickel-containing complex is preferably 2: 1; to obtain hollow ring-shaped MCC-Cu2MSn2S7Nanoparticles, preferably further comprising: mixing MCC-Cu2MSn2S7Heating the nano particles to obtain hollow annular MCC-Cu2MSn2S7Nanoparticles; the heating temperature is preferably 200 ℃, and the heating time is preferably 10-30 minutes;
step four: the MCC-Cu obtained in the third step2MSn2S7The nano particles are subjected to anti-precipitation purification by isopropanol to obtain Cu coated by the metal chalcogenide complex2MSn2S7Nanoparticles; the MCC-Cu2MSn2S7The volume ratio of the nanoparticles to the isopropanol is (1-3) to 1.
The invention also provides the metal chalcogenide complex coated nano particle obtained by the preparation method.
The invention also provides application of the metal chalcogenide complex-coated nano particles in the fields of aqueous phase inorganic nanocrystalline solar cells and electro-catalysis hydrogen production.
In order that the invention may be more clearly and specifically, reference will now be made to the following illustrative examples which are provided herein for the purpose of illustration only and are not intended to be limiting of the present invention.
Example 1
1. Synthesis of MCC ligands
35mL of 0.035mol/L Na2S·9H2O was added dropwise to 10mL of 0.035mol/L SnCl4·5H2Obtaining clear and transparent orange-yellow Sn in O solution2S7 6-An MCC ligand.
2. Synthesis of copper tetraammine and zinc tetraammine complexes
Several drops of concentrated ammonia were added to 0.125mol/L of Cu (Ac)2·H2O and 0.125mol/L Zn (Ac)2·2H2In the O solution, a dark blue tetraammine copper complex and a colorless and transparent tetraammine zinc complex are obtained.
3、MCC-Cu2ZnSn2S7Synthesis of (2)
2mL of the copper tetraammine complex was added dropwise to the MCC ligand, followed by 1mL of the zinc tetraammine complex to give a brownish red solution. Stirring for 30 minutes to obtain MCC-Cu2ZnSn2S7Nanoparticles.
4. With MCC-Cu2ZnSn2S7Adding isopropanol into isopropanol in a volume ratio of 3:1 for reverse precipitation, and then re-dissolving in water to obtain MCC-Cu with high purity and solubility2ZnSn2S7And (3) solution.
Electrocatalytic hydrogen production experiment
2mg of MCC-Cu prepared in example 12ZnSn2S7The nano particles are dissolved in 200 mu L of water, dropped on the ITO glass cleaned by the oxygen plasma, evenly coated and dried in an oven at 60 ℃. Then, the three-electrode reaction tank is used for testing the electro-catalytic hydrogen production activity under the condition that 0.5M sulfuric acid is used as electrolyte. The current density of the obtained polarization curve was measured to be-0.45 mA cm-2As shown in table 1.
FIG. 1 shows MCC-Cu prepared in example 12ZnSn2S7(ii) the (a) IR and (b) Raman spectra of the nanoparticles; as shown in FIG. 1a, in MCC-Cu2ZnSn2S7The infrared spectrum of NCs has a wavelength of 1500cm-1The absorption at 3500cm is mainly due to stretching vibration of Sn-S bond-1The left and right absorption comes from the stretching vibration of N-H/O-H, the infrared absorption spectrum of the sample is basically unchanged before and after the anti-precipitation, and obvious Sn-S bonds are detected. Further, in the Raman spectrum, it is located at 350cm-1Shows Sn2S7 6-And the diffraction peak at 400 to 450 indicates SxDemonstrates the successful formation of MCC ligands.
FIG. 2 shows MCC-Cu prepared in example 12ZnSn2S7XRD spectroscopy of the nanoparticles; as shown in fig. 2Shown is MCC-Cu2ZnSn2S7The nano particles respectively have a diffraction peak near 28 degrees and 47 degrees, the coincidence with standard card PDF #26-0575 is good, and no other impurity peak appears.
FIG. 3 shows MCC-Cu prepared in example 12ZnSn2S7TEM photograph of the nanoparticles; wherein the image a is a transmission electron micrograph at low magnification, and the image b is a high resolution micrograph, as shown in FIG. 3, MCC-Cu2ZnSn2S7The size of the nano particles is within 10nm, and the crystallinity is good.
FIG. 4 shows MCC-Cu prepared in example 12ZnSn2S7EDX data for nanoparticles; as shown in FIG. 4, MCC-Cu2ZnSn2S7The content ratios of the four elements of Cu, Zn, Sn and S in the nano particles are respectively 11.11%, 4.32%, 24.01% and 60.56%, and the nano particles are well matched with the feeding ratio and have no other impurity elements, so that the nano particles have high purity.
FIG. 7 is the MCC-Cu prepared in example 12ZnSn2S7XPS spectroscopy of the nanoparticles; wherein, the diagram a is Cu2p, the diagram b is Zn2p, the diagram c is Sn3d, the diagram d is S2p, as shown in FIG. 7, in MCC-Cu2ZnSn2S7The XPS spectra of the nanoparticles show the co-presence of Cu2p, Zn2p, Sn3d and S2 p.
Example 2
1. Synthesis of MCC ligands
35mL of 0.035mol/L Na2S·9H2O was added dropwise to 10mL of 0.035mol/L SnCl4·5H2Obtaining clear and transparent orange-yellow Sn in O solution2S7 6-An MCC ligand.
2. Synthesis of copper tetraammine and nickel tetraammine complexes
Several drops of concentrated ammonia were added to 0.125mol/L of Cu (Ac)2·H2O and 0.125mol/L of Ni (Ac)2·4H2In O solution, a dark blue tetraammine copper complex and a light blue tetraammine nickel complex are obtained.
3、MCC-Cu2NiSn2S7Synthesis of (2)
2mL of the tetraammine copper complex was added dropwise to the MCC ligand, followed by 1mL of the tetraammine nickel complex. Stirring for 30 minutes to obtain MCC-Cu2NiSn2S7Nanoparticles.
4. With MCC-Cu2NiSn2S7Adding isopropanol into isopropanol in a volume ratio of 3:1 for reverse precipitation, removing impurity ions, improving the solubility of the nanoparticles, and then re-dissolving in water to obtain MCC-Cu with high purity and solubility2NiSn2S7And (3) solution.
Electrocatalytic hydrogen production experiment
2mg of MCC-Cu prepared in example 22NiSn2S7The nano particles are dissolved in 200 mu L of water, dropped on the ITO glass cleaned by the oxygen plasma, evenly coated and dried in an oven at 60 ℃. Then, the three-electrode reaction tank is used for testing the electro-catalytic hydrogen production activity under the condition that 0.5M sulfuric acid is used as electrolyte. The current density of the obtained polarization curve was measured to be-1.75 mA cm-2As shown in table 1.
FIG. 5, panel a shows MCC-Cu prepared in example 22NiSn2S7Nanoparticles, shown in FIG. 5a, Cu2NiSn2S7Diffraction peak position and Cu in XRD spectrum of nano particle2ZnSn2S7The nanoparticles were shifted slightly to the right compared to the literature reports, consistent with the literature reports.
Example 3
1. Synthesis of MCC ligands
35mL of 0.035mol/L Na2S·9H2O was added dropwise to 10mL of 0.035mol/L SnCl4·5H2Obtaining clear and transparent orange-yellow Sn in O solution2S7 6-An MCC ligand.
2. Synthesis of copper tetraammine and cobalt tetraammine complexes
Several drops of concentrated ammonia were added to 0.125mol/L of Cu (Ac)2·H2O and 0.125mol/L of Co (Ac)2·4H2In O solution, a dark blue tetrammine copper complex and a wine red tetrammine are obtainedA cobalt complex.
3、MCC-Cu2CoSn2S7Synthesis of (2)
2mL of the tetraammine copper complex was added dropwise to the MCC ligand, followed by 1mL of the tetraammine cobalt complex to give a brownish red solution. Stirring for 30 minutes to obtain MCC-Cu2CoSn2S7Nanoparticles.
4. With MCC-Cu2CoSn2S7Adding isopropanol into isopropanol in a volume ratio of 3:1 for reverse precipitation, removing impurity ions, improving the solubility of the nanoparticles, and then re-dissolving in water to obtain MCC-Cu with high purity and solubility2CoSn2S7And (3) solution.
Electrocatalytic hydrogen production experiment
2mg of MCC-Cu prepared in example 32CoSn2S7The nano particles are dissolved in 200 mu L of water, dropped on the ITO glass cleaned by the oxygen plasma, evenly coated and dried in an oven at 60 ℃. Then, the three-electrode reaction tank is used for testing the electro-catalytic hydrogen production activity under the condition that 0.5M sulfuric acid is used as electrolyte. The current density of the obtained polarization curve was measured to be-5.55 mA cm-2As shown in table 1.
FIG. 5b is the MCC-Cu prepared in example 32CoSn2S7Nanoparticles, shown in FIG. 5b, Cu2CoSn2S7Diffraction peak position and Cu in XRD spectrum of nano particle2ZnSn2S7The nanoparticles were shifted slightly to the right compared to the literature reports, consistent with the literature reports.
FIG. 6 shows MCC-Cu prepared in examples 1 to 32MSn2S7UV profile of the nanoparticles; as shown in FIG. 6, MCC-Cu2MSn2S7The absorption range of the nano particles can cover the whole visible light region, and the nano particles have potential application in the field of photoelectricity.
Example 4
1. Synthesis of MCC ligands
35mL of 0.035mol/L Na2S·9H2O was added dropwise to 10mL of 0.035mol/L SnCl4·5H2Obtaining clear and transparent orange-yellow Sn in O solution2S7 6-An MCC ligand.
2. Synthesis of copper tetraammine and cobalt tetraammine complexes
Several drops of concentrated ammonia were added to 0.125mol/L of Cu (Ac)2·H2O and 0.125mol/L of Co (Ac)2·4H2In the O solution, a dark blue tetraammine copper complex and a wine red tetraammine cobalt complex are obtained.
3、MCC-Cu2CoSn2S7Synthesis of (2)
2mL of the tetraammine copper complex was added dropwise to the MCC ligand, followed by 1mL of the tetraammine cobalt complex to give a brownish red solution. Stirring for 30 minutes to obtain MCC-Cu2CoSn2S7Nanoparticles.
4. With MCC-Cu2CoSn2S7Adding isopropanol into isopropanol in a volume ratio of 3:1 for reverse precipitation, removing impurity ions, improving the solubility of the nanoparticles, and then re-dissolving in water to obtain MCC-Cu with high purity and solubility2CoSn2S7And (3) solution.
Electrocatalytic hydrogen production experiment
2mg of MCC-Cu prepared in example 42CoSn2S7The nano particles are dissolved in 200 mu L of water, dropped on the ITO glass cleaned by the oxygen plasma, evenly coated and dried in an oven at 60 ℃. And then testing the electro-catalytic hydrogen production activity by using a three-electrode reaction cell under the condition of taking 0.5M sodium sulfate as electrolyte. The current density of the obtained polarization curve was measured to be-5.55 mA cm-2As shown in table 1.
Example 5
1. Synthesis of MCC ligands
35mL of 0.035mol/L Na2S·9H2O was added dropwise to 10mL of 0.035mol/L SnCl4·5H2Obtaining clear and transparent orange-yellow Sn in O solution2S7 6-An MCC ligand.
2. Synthesis of copper tetraammine and zinc tetraammine complexes
Several drops of concentrated ammonia were added to 0.125mol/L of Cu (Ac)2·H2O and 0.125mol/L Zn (Ac)2·2H2In the O solution, a dark blue tetraammine copper complex and a colorless and transparent tetraammine zinc complex are obtained.
3. Hollow ring-shaped MCC-Cu2ZnSn2S7Synthesis of nanoparticles
Dropwise adding 2mL of tetraammine copper complex into the MCC ligand, adding 1mL of tetraammine zinc complex to obtain a brownish red solution, and stirring for 30 minutes to obtain MCC-Cu2ZnSn2S7Nano particles, heating the nano particles for 20 minutes at 200 ℃ to obtain hollow annular MCC-Cu2ZnSn2S7Nanoparticles.
4. Cooling to room temperature, adding MCC-Cu2ZnSn2S7Adding isopropanol in the volume ratio of 3:1 for reverse precipitation, removing impurity ions, improving the solubility of the nanoparticles, and dissolving in water again to obtain MCC-Cu with high purity and solubility2ZnSn2S7And (3) solution.
2mg of the hollow ring-shaped MCC-Cu prepared in example 52ZnSn2S7The nano particles are dissolved in 200 mu L of water, dropped on the ITO glass cleaned by the oxygen plasma, evenly coated and dried in an oven at 60 ℃. Then, the three-electrode reaction tank is used for testing the electro-catalytic hydrogen production activity under the condition that 0.5M sulfuric acid is used as electrolyte. The current density of the obtained polarization curve was measured to be-1.05 mA cm-2As shown in table 1.
FIG. 8 is a hollow ring-shaped MCC-Cu prepared in example 52ZnSn2S7TEM photograph of the nanoparticles; wherein, the picture a is a low magnification photograph, the picture b is a high resolution photograph, as shown in FIG. 8, MCC-Cu after heating at 200 deg.C2ZnSn2S7The nano particles present a hollow annular structure, have obvious lattice stripes and have the size of 20nm, which shows that the crystallinity and the particle size of the nano particles are improved in the heating process.
FIG. 9 shows examples 1 to 5Prepared MCC-Cu2MSn2S7Linear voltammograms of the nanoparticles; as shown in fig. 9, at 0.5M H2SO4As an electrolyte, Cu at a voltage of-0.8V2ZnSn2S7Hollow ring shaped Cu2ZnSn2S7、Cu2NiSn2S7And Cu2CoSn2S7The current density of the nanoparticles was-0.45 mA cm-2、-1.05mA cm-2、-1.75mA cm-2And-5.55 mA cm-2When using 0.5M Na2SO4When used as an electrolyte, Cu2CoSn2S7The current density of the nanoparticles at-0.8V was essentially unchanged.
Example 6 aqueous MCC-Cu2ZnSn2S7Inorganic nanocrystalline solar cell
2mg of MCC-Cu prepared in example 12ZnSn2S7The nanoparticles were dissolved in 200. mu.L of water and the TiO was then2The precursor was spin coated onto the oxygen plasma cleaned ITO glass at 2000 rpm. And then annealing the titanium dioxide film in the air at 450 ℃ for 15-20 minutes. Then MCC-Cu2ZnSn2S7The solution was spin coated onto the titanium dioxide film at 800rpm, annealed at 315 ℃ for 2 minutes in a glove box, and then spin coated with the second layer. And heating for 20-60 minutes after the spin coating is finished so as to ensure complete removal of the ligand and sufficient growth of crystals. Finally, MoO is evaporated by an evaporation instrument3And the Au anode were successively evaporated onto the active layer. Aqueous MCC-Cu2ZnSn2S7The NCs device has the structure of ITO/TiO2/Cu2ZnSn2S7/Cu2ZnSn2S7:PVP(50:0.5)/MoO3and/Au. Wherein, ITO, TiO2、Cu2ZnSn2S7、MoO3And Au is respectively used as a cathode, an electron transport layer, an active layer, a hole transport layer and an anode, and the device efficiency is 0.02%.
FIG. 10 is aqueous MCC-Cu prepared in example 62ZnSn2S7Current-to-current of NCs devicesPressing the curve; as shown in FIG. 10, aqueous MCC-Cu2ZnSn2S7NCs have obvious photovoltaic response capability, the voltage is 0.12V, and the current is 0.45mA cm-2The fill factor was 28.64%, and the photoelectric conversion efficiency was 0.02%.
TABLE 1
Composition of nanoparticles Kind of electrolyte Electrocatalytic hydrogen production current density
Example 1 Cu2ZnSn2S7 0.5M H2SO4 -0.45mA cm-2
Example 2 Cu2NiSn2S7 0.5M H2SO4 -1.75mA cm-2
Example 3 Cu2CoSn2S7 0.5M H2SO4 -5.55mA cm-2
Example 4 Cu2CoSn2S7 0.5M Na2SO4 -5.55mA cm-2
Example 5 Hollow ring shaped Cu2ZnSn2S7 0.5M H2SO4 -1.05mA cm-2
As can be seen from Table 1, the catalysts in examples 3 to 4 were Cu2CoSn2S7The catalytic hydrogen production effect is highest, and the photocurrent density can reach-5.55 mA cm-2. The electrocatalytic hydrogen production activity is mainly influenced by the composition of the nanoparticles.
In conclusion, the present invention prepares MCC-Cu with high concentration and solubility by a simple solution method2MSn2S7Nanoparticles. Simple operation, low toxicity and consumption, short experimental period (40 minutes), high yield and suitability for routine laboratory research. The obtained nano particles have wide application prospect in the photoelectric fields of electrocatalysis, solar cells and the like.

Claims (6)

1. A preparation method of metal chalcogenide complex coated nano particles is characterized by comprising the following steps:
the method comprises the following steps: dropwise adding the sulfide solution into the tin salt solution to obtain Sn2S7 6- An MCC ligand;
step two: adding concentrated ammonia water into a transition metal salt solution to obtain a transition metal complex; the transition metal salt solution is selected from copper salt and at least one of zinc salt, cobalt salt or nickel salt;
step three: dropwise adding the transition metal complex obtained in the step two into the ligand obtained in the step one, and stirring to obtain the MCC-Cu2MSn2S7Nanoparticles;
step four: the MCC-Cu obtained in the third step2MSn2S7The nano particles are subjected to anti-precipitation purification by isopropanol to obtain nano particles coated by the metal chalcogenide complex;
the volume ratio of the sulfide solution to the tin salt solution in the step is 7: 2;
the obtained MCC-Cu2MSn2S7After the nano particles, the MCC-Cu of the step three is also included2MSn2S7Heating the nano particles to obtain hollow annular MCC-Cu2MSn2S7Nanoparticles;
the heating temperature is 200 ℃, and the heating time is 10-30 minutes.
2. The method of claim 1, wherein the sulfide is sodium sulfide or potassium sulfide, and the tin salt is tin chloride or tin bromide.
3. The method of claim 1, wherein the copper salt is cupric chloride, cupric acetate, or cupric sulfate; the zinc salt is zinc chloride, zinc acetate or zinc sulfate; the cobalt salt is cobalt chloride, cobalt acetate or cobalt sulfate; the nickel salt is nickel chloride, nickel acetate or nickel sulfate.
4. The method as claimed in claim 1, wherein the concentration of the concentrated ammonia water in the second step is 13mol/L, and the concentration of the transition metal salt solution is 0.125 mol/L.
5. The metal chalcogenide complex coated nanoparticle of claim 1Is characterized in that the MCC-Cu of the step four2MSn2S7The volume ratio of the nanoparticles to the isopropanol is (1-3) to 1.
6. The application of the metal chalcogenide complex-coated nanoparticles prepared by the preparation method of claim 1 in the fields of aqueous phase inorganic nanocrystalline solar cells and electrocatalytic hydrogen production.
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