CN114147222A - Chiral metal-semiconductor heterogeneous nano material and preparation method thereof - Google Patents

Chiral metal-semiconductor heterogeneous nano material and preparation method thereof Download PDF

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CN114147222A
CN114147222A CN202111476766.3A CN202111476766A CN114147222A CN 114147222 A CN114147222 A CN 114147222A CN 202111476766 A CN202111476766 A CN 202111476766A CN 114147222 A CN114147222 A CN 114147222A
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chiral
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王鹏鹏
谭丽丽
李嘉明
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Xian Jiaotong University
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    • B22—CASTING; POWDER METALLURGY
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G5/00—Compounds of silver
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention provides a chiral metal-semiconductor heterogeneous nano material and a preparation method thereof, which comprises the steps of depositing Ag on a chiral metal nano material (such as a chiral gold nanorod, a chiral gold nano propeller and the like) to obtain a chiral metal-Ag intermediate; will handThe chiral metal-Ag is obtained by the reaction of the neutral metal-Ag intermediate and an anion precursor X (X is sulfur or selenium)2X semiconductor heterogeneous nanomaterials; adding chiral metal-Ag2And carrying out ion exchange on the X semiconductor heterogeneous nano material and the series semiconductor cation precursors to obtain a plurality of chiral metal-semiconductor heterogeneous nano materials. The invention uses Ag or Ag2The S buffer layer reduces the lattice mismatch degree among materials, realizes the construction and chiral coupling of the chiral metal-semiconductor heterogeneous nano material for the first time, derives a new optical effect while controllably changing a chiral signal, and opens up a new way for designing and developing novel inorganic chiral nano materials with easily controlled structures and adjustable optical activity.

Description

Chiral metal-semiconductor heterogeneous nano material and preparation method thereof
Technical Field
The invention belongs to the technical field of nano materials, and relates to a chiral metal-semiconductor heterogeneous nano material and a preparation method thereof.
Background
Chirality is a special asymmetry that an object and a mirror image thereof cannot coincide, and a chiral material with the property can show special optical, electrical, magnetic and other properties, and has been widely applied to the fields of information encryption, asymmetric catalysis, photoelectrocatalysis, biosensing, biotherapy, chiral photoelectric devices, polarization control display and the like in recent years, and has gained wide attention in different subject fields. At present, chiral substances based on organic materials have weak visible light response and poor stability; compared with organic micromolecules and macromolecules, inorganic materials (from a few nanometers to hundreds of nanometers) with equivalent dimension have the advantages of easily controlled structure and periodicity, good physicochemical property and optical stability and the like, are ideal research and application materials in the technical field of chiral materials, but the chiral property and the application of the materials are still limited at present. Wherein, the difficulty in preparing the inorganic chiral nano material, single species and poor controllability of chiral signals are main factors restricting the application and commercialization of the inorganic chiral nano material.
The chiral heterogeneous nano material is a novel composite material, and a chiral nano structure is combined with inorganic nano materials such as semiconductors, metals and the like, so that on one hand, a chiral signal can be regulated and controlled on a nano scale, on the other hand, the coupling effect between the chirality and other functions (such as photoelectric properties, magnetism, catalysis, plasmon polariton and the like) is realized, and new properties and related new applications thereof are developed. At present, the chirality of inorganic chiral nano materials mostly depends on surface chiral molecules or chiral soft and hard templates, which is not beneficial to the construction of heterogeneous materials and easily causes the phenomena of poor coupling of the heterogeneous materials, even disappearance of the chirality and the like. The metal nano structure with the chiral shape has high chiral activity and stable structure, and has the advantages of surface plasma resonance effect, photothermal effect, good biocompatibility and the like, so that the metal nano structure is considered to be one of better components for constructing a chiral inorganic heterojunction. At present, the improvement of chiral signals by constructing chiral metal heterogeneous nano materials through the combination of a plurality of metal components, such as chiral Au @ Ag core-shell satellite structures and chiral Au @ Cu @ Au heterogeneous nano materials, has been studied. However, these heterogeneous nanomaterials are still limited to the structure of the metal-metal component combination and have single functions, which restricts the further development and practical application of the chiral nanomaterials. Therefore, the development of a chiral heterojunction material for preparing metal and other functional materials and a universal method thereof are of great significance.
Disclosure of Invention
The invention aims to provide a chiral metal-semiconductor nano material which is simple and easy to control and a universal preparation method thereof. By combining chirality, surface plasmon resonance effect, photothermal effect, good biocompatibility and other properties of chiral metal (such as Au, Ag, Pt, Pd and the like) with semiconductor (such as oxide, sulfide, selenide, magnetic oxide such as CdS, CdSe, ZnS, Ag2S、Fe3O4、TiO2And the like) are combined with the advantages of optical, electrical, magnetic and the like, so that the difficulty of single structure of the chiral material can be solved, and the chiral material is favorable for realizing rich functionality. The method combines epitaxial growth with a chemical conversion method or a direct growth method to coat the semiconductor material on the surface of the chiral metal nano particle to form a tight interface, thereby overcoming the growth problem of a chiral heterostructure and effectively realizing the construction of the chiral metal-semiconductor nano material. The chiral heterogeneous nano material provided by the invention has the advantages that single or multiple parameters such as material type, morphology, size, shell thickness and integral chiral signals can be accurately controlled, the components have good synergistic effect, the optical activity and functionality of the chiral material can be greatly improved and controlled, and the application prospect is wide.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a chiral metal-semiconductor heterogeneous nano material and a preparation method thereof, wherein the preparation method comprises the following steps:
step 1, mixing an aqueous solution of an achiral metal nano material with chiral molecules for reaction to obtain a metal nano material modified by the chiral molecules, adding the metal nano material modified by the chiral molecules into a growth solution, and performing multi-degree growth for multiple times to obtain the chiral metal nano material;
step 2, dispersing the chiral metal nano material in the chiral shape into a surfactant solution, sequentially adding aqueous solutions of silver nitrate, ascorbic acid and sodium hydroxide, mixing, reacting, and centrifuging and washing to obtain a chiral metal-Ag intermediate;
step 3, preparing the chiral metal-Ag intermediate into a solution, adding a surfactant and an anion precursor, and mixing and reacting to obtain the chiral metal-Ag2X is a semiconductor heterogeneous nano material, and X is an anion;
step 4, the chiral metal-Ag2Preparing the X semiconductor heterogeneous nano material into a solution, dispersing the solution into a surfactant, sequentially adding a cation precursor and trioctylphosphine, and carrying out a cation exchange reaction to obtain the chiral metal-semiconductor heterogeneous nano material.
Preferably, in the step 1, the chiral metal nanomaterial is prepared according to the following method:
mixing and reacting an aqueous solution of an achiral metal nano material with chiral molecules to obtain a metal nano material modified by the chiral molecules, adding the metal nano material modified by the chiral molecules into a growth solution, and performing multi-degree growth for multiple times to obtain the chiral metal nano material.
The achiral metal nano material is a gold nanorod or a gold nanopyramid.
The chiral molecule is L-cysteine, D-cysteine, L-glutathione, D-glutathione, L-penicillamine or D-penicillamine;
the mass ratio of the achiral metal nano material to the chiral molecules is 1: (0.01-0.06).
The growth solution is prepared from a surfactant, chloroauric acid and ascorbic acid according to a molar ratio of 7: (6-10): 900.
The volume ratio of the metal nano material solution modified by the chiral molecules to the growth solution is 1: (16-24).
Preferably, the mixing reaction time of the achiral metal nano material and the chiral molecules is 0.5-2 h; the mixing reaction temperature is 30-60 ℃.
The mixing reaction time of the metal nano material solution modified by the chiral molecules and the growth solution is 0.5-2 h, and the number of overgrowth times is 1-5.
Preferably, the chiral metal nanomaterial is a chiral gold nanorod, a chiral gold polyhedron, or a chiral gold propeller nanomaterial.
Preferably, in the step 2, the chiral metal nano material is dispersed in water to prepare a chiral metal nano material solution with a concentration of 0.03-0.05 mg/mL.
The volume ratio of the chiral metal nano material solution to the surfactant to the silver nitrate solution to the ascorbic acid solution to the sodium hydroxide solution is 150: (20-120): 4: 1: 2.
the reaction temperature is 30-60 ℃; the reaction time is 0.5-1 h.
Preferably, in the step 3, the concentration of the chiral metal-Ag intermediate solution is 0.03-0.05 mg/mL;
the volume ratio of the chiral metal-Ag intermediate solution to the surfactant solution to the anion precursor is 3: 1: (0.01-0.02);
the anion precursor is a sulfur or selenium precursor solution; the reaction temperature is 30-50 ℃; the reaction time is 0.5-1.5 h;
the chiral metal-Ag2The X semiconductor heterogeneous nano material is chiral metal-Ag2S semiconductor heterogeneous nano material or chiral metal-Ag2Se semiconductor heterogeneous nano material.
Preferably, in the step 4, chiral metal-Ag2Dispersing the X semiconductor heterogeneous nano material in water to prepare a solution with the concentration of 0.03-0.05 mg/mL;
chiral metal-Ag2The volume ratio of the X semiconductor heterogeneous nano material solution to the surfactant solution to the cationic precursor solution to the trioctylphosphine is 3: 1: (0.05-0.09): (0.004-0.01).
The molar concentration of the surfactant solution is 0.08-0.2M.
The mass concentration of the cation precursor solution is 50 mg/mL.
The reaction temperature is 30-160 ℃; the reaction is carried out for 0.5-4 h.
The cation precursor is cadmium nitrate, zinc nitrate, indium nitrate or mercury nitrate.
The chiral metal-semiconductor heterogeneous nano material is a chiral Au-CdS heterogeneous nano material, a chiral Au-CdSe heterogeneous nano material, a chiral Au-ZnS heterogeneous nano material, a chiral Au-ZnSe heterogeneous nano material or a chiral Au-InS heterogeneous nano materialxA heterogeneous nanomaterial.
Preferably, the surfactant is cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
In a second aspect, the preparation method comprises the steps of preparing chiral metal nano materials, chiral metal-Ag intermediates and chiral metal-semiconductor nano materials with chiral shapes. Metal nanomaterials having chiral shapes and chiral metal-semiconductor hetero nanomaterials formed based thereon.
The chiral metal nanostructure provided by the invention induces the structural distortion thereof through the chiral ligand, thereby generating an intrinsic chiral shape. The chiral ligand is not contained within the nanomaterial.
In a third aspect, the chiral metal-semiconductor heterogeneous nano material prepared by the method can be applied to asymmetric catalysis, photoelectric energy catalysis, biosensing, biotherapy, chiral photoelectric devices and polarization control display.
The invention has the beneficial effects that: the chiral metal nano material with a chiral shape, such as a chiral propeller structure, a chiral polyhedral structure, a chiral twisted nanorod and the like, is synthesized for the first time, and has two circular dichroism characteristic peaks and good stability in a visible region. The simple and efficient overgrowth reduction method is adopted, harsh experimental conditions such as high temperature and high pressure and complex synthesis devices are not involved, the operation is simple, and the cost is low. In addition, the chiral metal-semiconductor heterogeneous nano material is synthesized for the first time, the inner core is in close contact with the outer shell, the interaction is strong, the new optical property is coupled while the good chiral signal is shown, and the metal property and the semiconductor function are fused, so that the application field of the chiral nano material is greatly expanded.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 is a transmission electron microscope image of chiral gold nanorods of the invention;
FIG. 2 is a three-dimensional reconstructed photograph of chiral gold nanorods of the present invention;
FIG. 3 is a circular dichroism spectrum of chiral gold nanorods of the invention;
FIG. 4 is a transmission electron microscope image of a chiral gold polyhedron of the present invention;
FIG. 5 is a transmission electron micrograph of a chiral gold propeller of the present invention;
FIG. 6 is a transmission electron microscope image of the chiral gold-silver nanorod of the invention;
FIG. 7 is a transmission electron microscope image of a chiral gold-silver sulfide heterostructure of the present invention;
FIG. 8 is a circular dichroism spectrum of a chiral gold-silver sulfide heterogeneous nanostructure of the present invention;
FIG. 9 is a transmission electron microscope image of a chiral gold-silver sulfide core-shell polyhedron of the present invention;
FIG. 10 is a transmission electron microscope image of a chiral gold-silver sulfide core-shell propeller of the present invention;
FIG. 11 is a transmission electron microscope image of a chiral gold-zinc sulfide hetero-nanostructure of the present invention
FIG. 12 is a transmission electron microscope image of a chiral gold-cadmium sulfide core-shell nanostructure of the present invention;
FIG. 13 is an energy spectrum of a chiral gold-cadmium sulfide core-shell nanostructure of the present invention;
FIG. 14 is a circular dichroism spectrum of a chiral gold-cadmium sulfide core-shell nanostructure of the present invention;
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the present invention are provided to explain the present invention without limiting the invention thereto.
The invention provides a preparation method of a chiral metal-semiconductor heterogeneous nano material, which comprises a chiral metal nano material with a chiral shape, a chiral metal-Ag intermediate and a chiral metal-Ag2X heterogeneous nanomaterials and chiral metal-semiconductor nanomaterials.
In one embodiment, a chiral metal-semiconductor hetero nanomaterial is prepared:
1) preparing a chiral metal nano material:
reaction vessel treatment: soaking glassware in aqua regia for 10-12 h, washing with clear water and deionized water, soaking, and drying for subsequent experiments;
mixing an achiral metal nano material and chiral molecules according to a mass ratio of 1: (0.01-0.06) mixing and reacting for 0.5-2 h at 30-60 ℃; obtaining a solution of the metal nano material modified by the chiral molecules, and then mixing the solution of the metal nano material modified by the chiral molecules with a growth solution according to the volume ratio of 1: (16-24) mixing, and carrying out multiple overgrowth under the condition of 30-60 ℃, wherein the reaction time is 0.5-2 h, and the overgrowth times are 1-5; and centrifuging, washing and collecting the precipitate to obtain the chiral metal nano material precipitate.
Wherein the achiral metal nano material is a gold nanorod or a gold nanotriangle plate;
the chiral molecule is L-cysteine, D-cysteine, L-glutathione, D-glutathione, L-penicillamine or D-penicillamine;
the growth solution is prepared from a surfactant, chloroauric acid and ascorbic acid according to a molar ratio of 7: (6-10): 900 of the mixed solution;
the chiral metal nano material is a chiral gold nanorod, a chiral gold polyhedron or a chiral gold propeller nano material.
2) Preparation of chiral metal-Ag intermediate:
and (2) preparing a chiral metal nano material solution with the concentration of 0.03-0.05 mg/mL in the obtained chiral metal nano material precipitate dispersion water, and then mixing the chiral metal nano material solution, a surfactant, a silver nitrate solution, an ascorbic acid solution and a sodium hydroxide solution according to the volume ratio of 150: (20-120): 4: 1: 2, mixing, reacting for 0.5-1 h at 30-60 ℃, and centrifugally washing to obtain the chiral metal-Ag intermediate precipitate.
3) Chiral metal-Ag2Preparing an X heterogeneous nano material:
dispersing the chiral metal-Ag intermediate precipitate in water to prepare a solution with the concentration of 0.03-0.05 mg/mL; then, mixing the chiral metal-Ag intermediate solution, the surfactant solution and the anion precursor according to a volume ratio of 3: 1: (0.01-0.02), reacting for 0.5-1.5 h at 30-50 ℃, and centrifugally washing to obtain the chiral metal-Ag2And (3) X heterogeneous nano materials.
Wherein the surfactant is cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride.
The anion precursor is sulfur or selenium precursor solution.
Chiral metal-Ag2The X semiconductor heterogeneous nano material is chiral metal-Ag2S semiconductor heterogeneous nano material or chiral metal-Ag2Se semiconductor heterogeneous nano material.
4) Preparation of chiral metal-semiconductor heterogeneous nano material
Adding chiral metal-Ag2The X semiconductor heterogeneous nano material is dispersed in water to prepare chiral metal-Ag with the concentration of 0.03-0.05 mg/mL2X semiconductor heterogeneous nano material solution, and then adding chiral metal-Ag2The method comprises the following steps of (1) mixing an X semiconductor heterogeneous nano material solution, a surfactant with the molar concentration of 0.08-0.2M, a cation precursor solution with the mass concentration of 50mg/mL and trioctylphosphine according to the volume ratio of 3: 1: (0.05-0.09):
(0.004-0.01) mixing, and reacting for 0.5-4 h at the temperature of 30-160 ℃; and (4) centrifugally washing to obtain the chiral metal-semiconductor heterogeneous nano material.
Wherein the cation precursor is cadmium nitrate, zinc nitrate, indium nitrate or mercury nitrate.
The surfactant is cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride.
Chiral metal-semiconductor heteroThe material can be chiral metal-sulfide, chiral metal-selenide, etc., such as chiral Au-CdS, chiral Au-CdSe, chiral Au-ZnS, chiral Au-ZnSe, or chiral Au-InSxHeterogeneous nanomaterials, and the like.
The invention is further illustrated by the following specific examples.
Examples 1-5 are typical methods for the preparation of chiral metal nanomaterials.
Example 1 preparation of chiral metal nanomaterial (chiral Au nanorod):
mixing achiral gold nanorods with an L-cysteine solution with the concentration of 1mM according to the mass ratio of 1:0.01, reacting for 1h at 35 ℃ to obtain a chiral molecule modified gold nanorod solution, and mixing the chiral molecule modified gold nanorod solution with a molar ratio of 7: 6: 900 parts by volume of a growth solution of cetyltrimethylammonium chloride, chloroauric acid and ascorbic acid in a ratio of 1: 20, reacting for 0.5h at 60 ℃, centrifuging and washing twice, continuously repeating the growth steps to perform overgrowth of the gold nanostructure for 3 times in order to eliminate the influence of chiral molecules and make the chiral gold helical appearance more obvious.
The transmission electron microscope photo of the prepared chiral gold nanorod is shown in figure 1, and a dumbbell structure with two large ends and a small middle part is shown; the three-dimensional reconstructed photograph is shown in fig. 2, and the gold nanorods have a twisted structure; the circular dichroism spectrum is shown in figure 3, and the circular dichroism spectrums of the L-gold nanorods and the D-gold nanorods are in mirror symmetry; the peak values of the L-gold nanorods occur at 537nm (-50mdeg) and 639nm (50mdeg), respectively.
Example 2 preparation of chiral metal nanomaterials (chiral Au polyhedral nanomaterials):
the difference from the example 1 is that chiral gold polyhedral nano-materials are obtained by adopting different mass ratios, reaction temperatures, reaction times or growth times.
The method comprises the following specific steps: the method comprises the following steps of (1) mixing achiral gold nanorods with a D-cysteine solution with the concentration of 1mM in a mass ratio of 1: 0.06, reacting for 1h at 60 ℃ to obtain a chiral molecule modified gold nanorod solution, and mixing the chiral molecule modified gold nanorod solution with a molar ratio of 7: 10: 900 parts by volume of a growth solution of cetyltrimethylammonium bromide, chloroauric acid and ascorbic acid: 16, reacting for 1h at 40 ℃, centrifuging and washing twice, continuously repeating the growth steps for 2 times of overgrowth of the gold nanostructure in order to eliminate the influence of chiral molecules and make the chiral gold helical appearance more obvious.
The transmission electron microscope of the prepared chiral Au polyhedral nano material is shown in figure 4, the length of the transmission electron microscope is about 60nm, and the transmission electron microscope is provided with a plurality of twisted edges.
Example 3 preparation of chiral metal nanomaterials (chiral Au propeller nanomaterials):
the essential difference from examples 1 and 2 is that the achiral gold nanorods are replaced by achiral gold nanopyramids.
Mixing achiral gold nano triangular plate with 1mM L-glutathione according to the mass ratio of 1: 0.02, reacting for 2 hours at 50 ℃ to obtain a chiral molecule modified gold nanoparticle triangular plate solution, and mixing the chiral molecule modified gold nanoparticle triangular plate solution with a molar ratio of 7: 8: 900 parts by volume of a growth solution of cetyltrimethylammonium chloride, chloroauric acid and ascorbic acid in a ratio of 1: 24, reacting for 1.5h at 30 ℃, centrifuging and washing twice, continuously repeating the growth steps to perform overgrowth of the gold nanostructure for 2 times in order to eliminate the influence of chiral molecules and make the chiral gold helical appearance more obvious.
The transmission electron microscope photo of the prepared chiral Au propeller nano material is shown in FIG. 5, wherein the side length of the triangular plate is about 65nm, three angles are twisted in one direction, and the shape of the triangular plate is similar to that of a propeller.
Example 4 preparation of chiral metal nanomaterial (chiral Au nanorod):
the differences from example 1 are that different mass ratios, reaction temperatures, reaction times or growth times are used.
Mixing achiral gold nanorods with a D-glutathione solution with the concentration of 1mM according to the mass ratio of 1:0.05, reacting for 1.5h at 40 ℃ to obtain a chiral molecule modified gold nanorod solution, and mixing the chiral molecule modified gold nanorod solution with a solution of the D-glutathione with the molar ratio of 7: 10: 900 parts by volume of a growth solution of cetyltrimethylammonium chloride, chloroauric acid and ascorbic acid in a ratio of 1: 18, reacting for 0.8h at 40 ℃, centrifuging and washing twice, continuously repeating the growth steps to perform overgrowth of the gold nanostructure for 5 times in order to eliminate the influence of chiral molecules and make the chiral gold helical appearance more obvious.
Example 5 preparation of chiral metal nanomaterials (chiral Au propeller nanomaterials):
the difference from example 3 is that different mass ratios of achiral gold nanorods and chiral molecular reactants, reaction temperatures, reaction times or growth times are used. The specific experimental steps are as follows:
mixing an achiral gold nano triangular plate with D-penicillamine with the concentration of 1mM according to the mass ratio of 1: 0.03, reacting for 0.5h at 30 ℃ to obtain a chiral molecule modified gold nanoparticle triangular plate solution, and mixing the chiral molecule modified gold nanoparticle triangular plate solution with a molar ratio of 7: 7: 900 parts by volume of a growth solution of cetyltrimethylammonium chloride, chloroauric acid and ascorbic acid in a ratio of 1: 22, reacting for 1.6h at 50 ℃, centrifuging and washing twice, continuously repeating the growth steps to perform overgrowth of the gold nanostructure for 1 time in order to eliminate the influence of chiral molecules and make the chiral gold helical appearance more obvious.
From the above experimental results, it can be analyzed that: the chiral metal nano material with distorted appearance can be obtained by adsorbing and treating the metal nano material by using chiral molecules in advance and then overgrowing.
Examples 6-10 are typical methods for the preparation of chiral metal-Ag intermediates.
The chiral metal nanomaterial of any one of examples 1-5 (but not limited to the examples) is subjected to the preparation of a chiral metal-Ag intermediate.
Example 6 preparation of chiral metal-Ag intermediate (chiral Au-Ag nanorods):
in order to prepare the chiral metal-semiconductor nano material subsequently, the chiral Au-Ag nanorod is prepared firstly, and the process for synthesizing the chiral Au-Ag nanorod specifically comprises the following steps: the obtained chiral metal nanomaterial (any one of the chiral gold nanorods obtained in examples 1 to 5) was precipitated and dispersed in water to prepare a chiral metal nanomaterial solution with a concentration of 0.03mg/mL, and then the chiral metal nanomaterial solution, a cetyltrimethylammonium bromide solution with a concentration of 0.2M, silver nitrate with a concentration of 0.01M, an ascorbic acid solution with a concentration of 0.1M, and a sodium hydroxide solution with a concentration of 0.2M were mixed in a volume ratio of 150: 50: 4: 1: 2, mixing, reacting for 0.5h at 30 ℃, and then carrying out centrifugal washing to obtain the chiral Au-Ag nanorod with a tight interface.
The transmission electron micrograph of the chiral Au-Ag intermediate is shown in FIG. 6, and the interface formed by epitaxial growth is in close contact.
Example 7 preparation of chiral metal-Ag intermediate (chiral Au-Ag polyhedra):
the difference from the embodiment 6 is that the chiral gold nanorods are replaced by chiral gold polyhedrons, and the chiral Au-Ag polyhedrons can be obtained by the same experimental process as the embodiment 6.
Example 8 preparation of chiral metal-Ag intermediate (chiral Au-Ag nanoprism):
the difference from the embodiment 6 is that the chiral gold nanorods are replaced by chiral gold propellers, and the chiral Au-Ag nano propellers can be obtained by the same experimental process as the embodiment 6.
Example 9 preparation of chiral metal-Ag intermediate (chiral Au-Ag nanorods):
in order to prepare the chiral metal-semiconductor nano material subsequently, the chiral Au-Ag nanorod is prepared firstly, and the process for synthesizing the chiral Au-Ag nanorod specifically comprises the following steps: the obtained chiral metal nanomaterial (the chiral gold nanorods obtained in example 1) is precipitated and dispersed in water to prepare a chiral metal nanomaterial solution with a concentration of 0.05mg/mL, and then the chiral metal nanomaterial solution, a cetyl trimethyl ammonium bromide solution with a concentration of 0.2M, silver nitrate with a concentration of 0.01M, an ascorbic acid solution with a concentration of 0.1M, and a sodium hydroxide solution with a concentration of 0.2M are mixed according to a volume ratio of 150: 120: 4: 1: 2, mixing, reacting for 1h at 50 ℃, and then carrying out centrifugal washing to obtain the chiral Au-Ag nanorod with a tight interface.
Example 10 preparation of chiral metal-Ag intermediate (chiral Au-Ag nanoprism):
and (2) preparing a chiral gold propeller material solution with the concentration of 0.05mg/mL by dispersing the obtained chiral gold propeller material precipitate in water, and then mixing the chiral gold propeller material solution, a hexadecyl trimethyl ammonium chloride solution with the concentration of 0.2M, silver nitrate with the concentration of 0.01M, an ascorbic acid solution with the concentration of 0.1M and a sodium hydroxide solution with the concentration of 0.2M according to the volume ratio of 150: 20: 4: 1: 2, mixing, reacting at 60 ℃ for 0.8h, and then carrying out centrifugal washing to obtain the chiral Au-Ag core-shell nano propeller material.
Examples 11 to 16 are chiral metals-Ag2Typical preparation method of X heterogeneous nano material.
The chiral metal-Ag intermediate of any one of examples 6-10 was subjected to the following chiral metal-Ag2And preparing the X heterogeneous nano material.
Example 11 chiral Metal-Ag2X heterogeneous nanomaterial (chiral Au-Ag)2S heterogeneous nano rod) preparation:
dispersing the chiral metal-Ag intermediate precipitate (any one of the chiral Au-Ag nanorods obtained in examples 4-10) in water to prepare a solution with a concentration of 0.03 mg/mL; then, mixing the chiral metal-Ag intermediate solution, a 0.2M hexadecyl trimethyl ammonium bromide solution and a sulfur precursor solution according to a volume ratio of 3: 1: 0.018 mixing, reacting for 0.5h at 30 ℃, centrifuging and washing to obtain chiral Au-Ag2S heterogeneous nano-rods.
Chiral Au-Ag2The transmission electron micrograph of the S heterogeneous nanorod is shown in FIG. 7, and the chiral Au-Ag can be found2The inner core of the S heterogeneous nanorod is a chiral Au nanorod, and the shell of the S heterogeneous nanorod is Ag with the thickness of 6nm2S nano material; a series of chiral Au-Ag with different shell thicknesses2The circular dichroism spectrum of the S heterogeneous nanorod is shown in figure 8, when the shell thickness is 3nm, chiral characteristic peaks are positioned at 546nm, 605nm and 701nm, the intensities are respectively 34mdeg, -142mdeg and 89mdeg, and along with Ag2The thickness of the S shell is increased from 1.5nm to 6nm, the circular dichroism signal is gradually enhanced, and the thickness of the semiconductor shell layer is proper to ensure that the heterojunction materialThe two circular dichroism characteristic peaks of the material are split into three characteristic peaks, namely, a new chiral signal peak is derived from the heterojunction material.
Example 12 chiral Metal-Ag2X heterogeneous nanomaterial (chiral Au-Ag)2S core-shell polyhedrons):
the difference from the embodiment 11 is that the chiral Au-Ag nanorods in the experimental steps are replaced by any one of the chiral Au-Ag polyhedrons in the embodiments 6-10, and the chiral Au-Ag nanorods can be obtained by the rest of the experimental processes which are the same as the embodiment 112S core-shell polyhedrons.
The prepared chiral Au-Ag2FIG. 9 shows a transmission electron micrograph of the S-core polyhedron, chiral Au-Ag2The S core-shell polyhedron has the length of about 50nm and the width of about 40nm, and has an obvious core-shell structure and the shell thickness of about 5 nm.
Example 13 chiral Metal-Ag2X heterogeneous nanomaterial (chiral Au-Ag)2S core-shell propeller):
the difference from the embodiment 11 is that the chiral Au-Ag nanorod in the experimental step is replaced by the chiral Au-Ag propeller, and the chiral Au-Ag nanorod can be obtained by the rest of the experimental processes which are the same as those in the embodiment 112S core-shell propeller.
The prepared chiral Au-Ag2The transmission electron microscope photo of the S core-shell propeller is shown in figure 10, the shape of the S core-shell propeller is similar to that of a propeller, the S core-shell propeller has a compact core-shell structure, and the shell layer is about 10 nm.
Example 14 chiral Metal-Ag2X heterogeneous nanomaterial (chiral Au-Ag)2Se heterogeneous nano-rod):
the only difference from example 11 is that chiral Au-Ag can be obtained by replacing the sulfur precursor in the experimental step with a selenium precursor2Se heterogeneous nano-rods.
Example 15 chiral Metal-Ag2X heterogeneous nanomaterial (chiral Au-Ag)2S heterogeneous nano rod) preparation:
the difference from example 11 is that the reaction parameters are controlled, such as the concentration of chiral Au-Ag nanorod solution is 0.05mg/mL, the chiral metal-Ag intermediate solution/cetyl trimethyl ammonium bromide solution with concentration of 0.2M/sulfur precursorThe volume ratio of the bulk solution is 3: 1: 0.02 at 45 ℃ for 1.5h to obtain chiral Au-Ag2S heterogeneous nano-rods.
Example 16 chiral Metal-Ag2X heterogeneous nanomaterial (chiral Au-Ag)2S core-shell polyhedrons):
the difference from example 11 is that the chiral Au-Ag nanorods were replaced with any one of the chiral Au-Ag polyhedrons of examples 6-10, and the reaction parameters were adjusted such that the chiral Au-Ag polyhedral solution concentration was 0.035mg/mL, the chiral metal-Ag intermediate solution/hexadecyltrimethylammonium bromide solution/sulfur precursor solution having a concentration of 0.2M had a volume ratio of 3: 1:0.01, the reaction temperature is 50 ℃, the reaction time is 1h, and chiral Au-Ag is obtained2S-heteromorphic polyhedron.
From the above experimental results, it can be analyzed that: preparing a chiral Au-Ag heterostructure (chiral noble metal heterogeneous intermediate) by using gold and silver with proper lattice matching degree by adopting an epitaxial growth method for a chiral gold nano material with a chiral shape, and then vulcanizing to convert the chiral Au-Ag heterostructure into chiral Au-Ag2And (S) a core-shell structure. In addition, due to the electromagnetic resonance coupling effect between gold and silver sulfide, the regulation and control of the circular dichroism signal can be realized by regulating and controlling the thickness of the silver sulfide shell.
Examples 17-19 are typical methods for the preparation of chiral metal-semiconductor hetero-nanomaterials.
The chiral metal-Ag of any one of examples 11 to 162X heterogeneous nanomaterial, proceeding with the following chiral metal-Ag2And preparing the X heterogeneous nano material.
Example 17 preparation of chiral metal-semiconductor hetero nanomaterial (chiral Au-ZnS nanorod):
chiral Au-Ag2The S nano-rod is dispersed in water to prepare chiral Au-Ag with the concentration of 0.04mg/mL2S semiconductor heterogeneous nano material solution, and then adding chiral Au-Ag2S semiconductor heterogeneous nano material solution, 0.2M hexadecyl trimethyl ammonium bromide solution, zinc nitrate solution and trioctyl phosphine according to the volume ratio of 3: 1: 0.08: 0.01, mixing and reacting for 0.5h at the temperature of 120 ℃; centrifugally washing to obtainA chiral Au-ZnS core-shell nanorod.
The transmission electron microscope photo of the prepared chiral Au-ZnS core-shell nanorod is shown in FIG. 11, which shows a core-shell structure, and the results of the above experiment can be analyzed to obtain: the invention prepares the chiral Au-ZnS core-shell nano material by a simple chemical conversion method based on the chiral metal nano material, and constructs a novel chiral metal-semiconductor core-shell nano structure in a breakthrough manner.
Example 18 preparation of chiral metal-semiconductor hetero nanomaterial (chiral Au-CdS hetero nanorod):
the difference from the embodiment 17 is that the cationic precursor zinc nitrate is replaced by cadmium nitrate, and the rest steps are the same, so as to obtain the chiral Au-CdS heterogeneous nanorod.
Example 19 preparation of chiral metal-semiconductor hetero nanomaterial (chiral Au-CdS hetero nanorod):
the difference from example 17 is that the cationic precursor zinc nitrate is replaced by cadmium nitrate and the reaction conditions are changed, such as chiral Au-Ag2The volume ratio of S semiconductor heterogeneous nano material solution/hexadecyl trimethyl ammonium bromide solution with the concentration of 0.2M/cadmium nitrate solution/trioctyl phosphine is 3: 1: 0.09: 0.01, the reaction temperature is 70 ℃, and the reaction time is 2 hours, so as to obtain the chiral Au-CdS heterogeneous nanorod.
The method comprises the following specific steps: adding chiral metal-Ag2The S core-shell nanorod material is dispersed in water to prepare chiral metal-Ag with the concentration of 0.03mg/mL2S core-shell nano-rod material solution, and then adding chiral metal-Ag2S, preparing a core-shell nanorod material solution, a 0.2M hexadecyl trimethyl ammonium bromide solution, a cadmium nitrate solution and trioctyl phosphine according to a volume ratio of 3: 1: 0.09: 0.01, mixing and reacting for 2 hours at the temperature of 70 ℃; and (4) centrifuging and washing to obtain the chiral Au-CdS heterogeneous nanorod material.
The transmission electron microscope photo and the energy spectrum photo (EDS) of the chiral Au-CdS heterogeneous nanorod material are respectively shown in FIGS. 12 and 13, wherein chiral gold is the core of the heterostructure, and cadmium sulfide is the shell of the heterostructure; the circular dichroism spectrum of the chiral Au-CdS heterogeneous nanorod material is shown in FIG. 14, and the characteristic peaks are located at 521nm, 576nm and 684nm and have the intensities of 15mdeg, -149mdeg and 116 mdeg.
From the above experimental results, it can be analyzed that: according to the invention, the chiral metal nano material with a chiral shape is subjected to chemical conversion to obtain the chiral metal-semiconductor heterogeneous nano material with a good interface contact shell structure in one step, so that a novel chiral metal-semiconductor core-shell nano structure is constructed in a breakthrough manner, the preparation method is simpler and more convenient, the batch production is facilitated, and the subsequent application is facilitated.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.

Claims (10)

1. A method for preparing a chiral metal-semiconductor heterogeneous nano material is characterized by comprising the following steps:
step 1, mixing an aqueous solution of an achiral metal nano material with chiral molecules for reaction to obtain a metal nano material modified by the chiral molecules, adding the metal nano material modified by the chiral molecules into a growth solution, and performing multi-degree growth for multiple times to obtain the chiral metal nano material;
step 2, preparing the chiral metal nano material in the chiral shape into a solution, sequentially adding a surfactant, silver nitrate, ascorbic acid and sodium hydroxide aqueous solution into the chiral metal solution, mixing and reacting, and then centrifugally washing to obtain a chiral metal-Ag intermediate;
step 3, preparing the chiral metal-Ag intermediate into a solution, adding a surfactant and an anion precursor into the chiral metal-Ag intermediate solution, and mixing and reacting to obtain the chiral metal-Ag2X is a semiconductor heterogeneous nano material, and X is an anion;
step 4, the chiral metal-Ag2Preparing the X semiconductor heterogeneous nano material into solution, dispersing the solution into a surfactant, sequentially adding a cation precursor and trioctylphosphine, and carrying out a cation exchange reaction to obtain the handAnd (3) a metal-semiconductor heterogeneous nano material.
2. The method for preparing a chiral metal-semiconductor heterogeneous nanomaterial according to claim 1, wherein in the step 1, the achiral metal nanomaterial is a gold nanorod or a gold nanosheet;
the chiral molecule is L-cysteine, D-cysteine, L-glutathione, D-glutathione, L-penicillamine or D-penicillamine;
the mass ratio of the achiral metal nano material to the chiral molecules is 1: (0.01-0.06);
the growth solution is prepared from a surfactant, chloroauric acid and ascorbic acid according to a molar ratio of 7: (6-10): 900 of the mixed solution;
the volume ratio of the metal nano material solution modified by the chiral molecules to the growth solution is 1: (16-24).
3. The method for preparing the chiral metal-semiconductor heterogeneous nano material according to claim 1, wherein in the step 1, the mixing reaction time of the achiral metal nano material and the chiral molecules is 0.5-2 h; the reaction temperature is 30-60 ℃;
the mixing reaction time of the metal nano material solution modified by the chiral molecules and the growth solution is 0.5-2 h, and the number of overgrowth times is 1-5.
4. The method for preparing a chiral metal-semiconductor heterogeneous nanomaterial according to claim 1, wherein the chiral metal nanomaterial is a chiral gold nanorod, a chiral gold polyhedron, or a chiral gold propeller nanomaterial.
5. The method for preparing the chiral metal-semiconductor heterogeneous nanomaterial according to claim 1, wherein in the step 2, the chiral metal nanomaterial is dispersed in water to prepare a chiral metal nanomaterial solution with a concentration of 0.03-0.05 mg/mL;
the volume ratio of the chiral metal nano material solution to the surfactant to the silver nitrate solution to the ascorbic acid solution to the sodium hydroxide solution is 150: (20-120): 4: 1: 2;
the reaction temperature is 30-60 ℃; the reaction time is 0.5-1 h.
6. The method for preparing the chiral metal-semiconductor heterogeneous nanomaterial according to claim 1, wherein in the step 3), the concentration of the chiral metal-Ag intermediate solution is 0.03-0.05 mg/mL;
the volume ratio of the chiral metal-Ag intermediate solution to the surfactant solution to the anion precursor is 3: 1: (0.01-0.02);
the anion precursor is a sulfur or selenium precursor solution; the reaction temperature is 30-50 ℃; the reaction time is 0.5-1.5 h;
the chiral metal-Ag2The X semiconductor heterogeneous nano material is chiral metal-Ag2S semiconductor heterogeneous nano material or chiral metal-Ag2Se semiconductor heterogeneous nano material.
7. The method for preparing chiral metal-semiconductor heterogeneous nano-material according to claim 1, wherein in the step 4, chiral metal-Ag is added2Dispersing the X semiconductor heterogeneous nano material in water to prepare a solution with the concentration of 0.03-0.05 mg/mL;
chiral metal-Ag2The volume ratio of the X semiconductor heterogeneous nano material solution to the surfactant solution to the cationic precursor solution to the trioctylphosphine is 3: 1: (0.05-0.09): (0.004-0.01);
the molar concentration of the surfactant solution is 0.08-0.2M;
the mass concentration of the cation precursor solution is 50 mg/mL;
the reaction temperature is 30-160 ℃; reacting for 0.5-4 h;
the cation precursor is cadmium nitrate, zinc nitrate, indium nitrate or mercury nitrate;
the chiral metal-semiconductor heterogeneous nano material is a chiral Au-CdS heterogeneous nano material, a chiral Au-CdSe heterogeneous nano material, a chiral Au-ZnS heterogeneous nano material or a chiral metal-semiconductor heterogeneous nano materialChiral Au-InS or Au-ZnSe heterogeneous nano materialxA heterogeneous nanomaterial.
8. The method for preparing the chiral metal-semiconductor heterogeneous nanomaterial according to any one of claims 2, 5, 6 and 7, wherein the surfactant is cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
9. A chiral metal-semiconductor hetero nanomaterial prepared by the method of any one of claims 1 to 7.
10. The chiral metal-semiconductor heterogeneous nanomaterial of claim 9, which is applied to asymmetric synthesis, photoelectric energy catalysis, chiral sensing, biological diagnosis and treatment, chiral photoelectric devices and polarization control display.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114573016A (en) * 2022-03-11 2022-06-03 江南大学 Ag with chiral optical activityxCdyPreparation method and application of S-AgCd nanoparticles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114573016A (en) * 2022-03-11 2022-06-03 江南大学 Ag with chiral optical activityxCdyPreparation method and application of S-AgCd nanoparticles

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