CN106629815B - A kind of semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure and preparation method thereof - Google Patents

Abstract

The invention provides a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction chamber structure and a preparation method thereof. In situ partial sulfurization of solid Cu ₂ O nanocrystals or Cu ₂ O shell of solid Au@Cu ₂ O core-shell nanocrystals using Na ₂ S aqueous solution to make solid Cu ₂ O nanocrystals or Au@Cu ₂ O core-shell nanocrystals, transforming into Cu ₂ O/Cu ₂ S or Au/Cu ₂ S heterogeneous nanocrystals with hollow micro-reaction cavity structure and maintaining the shape; then using cationic reaction to transform the outer layer of Cu ₂ S into other Chalcogenide semiconductors, obtain semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure, in which the core of the micro-cavity is Cu ₂ O or Au nanocrystals, and the outer layer is a sulfide semiconductor, preferably CdS, ZnS, Cu ₂ S, SnS . The method of the invention is simple, the material composition and shape of the inner core and the outer layer can be adjusted, and a micro-reaction chamber is provided for heterogeneous catalysis, catalytic organic synthesis, sustained drug release and the like.

Description

A semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure and its preparation method

technical field

The present invention relates to the field of nanocrystalline materials with novel nano-morphology and controlled synthesis, in particular to nanocrystalline materials with heterogeneous structures, in particular to a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure and a preparation method thereof; Nanocrystalline materials can be used in photothermal conversion, photocatalytic degradation of dyes and other fields.

Background technique

Nanocrystals with a hollow microreaction chamber structure are very important nanocrystal materials, which can provide microreaction chambers for chemical reactions in heterogeneous catalysis, catalytic organic synthesis, drug sustained release, electrochemical cells, etc., and then in these It has a wide range of application value and is a hot topic in the synthesis and preparation of nanomaterials. First of all, nanocrystals with a hollow microreaction cavity structure are widely used in catalysis, such as photothermal conversion, photocatalytic degradation of dyes, photocatalytic synthesis, selective catalytic oxidation or reduction, electrode materials for lithium-ion batteries, sodium ions Battery electrode materials, drug sustained release materials, etc. In recent years, since the cavity between the inner core and the outer layer of this structure can be used as a microreactor, many new catalysts have been designed with this structure to improve the selectivity of the catalytic reaction. The hollow micro-reaction cavity structure of this kind of nanocrystal can also be designed by means of the pore size of its shell, so that only some molecules or reaction intermediates can enter the micro-nano reactor to improve the selectivity of the reaction. The design of catalysts with this structure And synthesis has also attracted the interest of the majority of catalytic chemists.

In the current research, the method of synthesizing nanocrystals with a hollow micro-reaction cavity structure is mainly to grow directly on the hollow structure or to modify or treat the outer layer on the basis of forming a core-shell structure. Another common synthesis method is The micro-reaction cavity is formed by introducing an intermediate layer during the construction of the core-shell structure, and finally removing the intermediate layer by means of thermal decomposition or corrosion. The preparation process of these methods is very cumbersome, and the prepared nanocrystals do not have good crystallinity, which seriously restricts the application of the obtained nanocrystals with a hollow micro-reaction cavity structure. In particular, such nanocrystals currently reported are mainly oxide/oxide, metal/oxide heterogeneous nanocrystals, and more types of metal/semiconductors. Nanocrystals of oxide/semiconductor structures are scarce, but these combinations produce The semiconductor-based heterogeneous nanocrystals with hollow microreaction cavity structure have great potential application value in catalysis, energy storage, coupling of different properties, surface plasmon effect and other applications. Therefore, how to provide a new, universal, and universal method for preparing metal/semiconductor and metal oxide/semiconductor heterogeneous nanocrystals with a hollow micro-reaction cavity structure has very important application value.

Contents of the invention

Aiming at the defects existing in the prior art, the present invention provides a semiconductor-based heterogeneous nanocrystal (including metal/semiconductor, metal oxide/semiconductor combination) with a hollow micro-reaction cavity structure and a universal preparation method thereof. The operation is simple, and the semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction chamber structure can be obtained with different combinations and adjustable micro-reaction chamber structures by adjusting the preparation conditions.

The present invention provides a new method for preparing semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure. The method can be generally applicable in the field of synthesis of such nanocrystals, and is prepared by using the preparation method described in the present invention. The semiconductor-based heterogeneous nanocrystals with a hollow microreaction cavity structure can have a wide range of applications in the fields of photocatalytic degradation of dyes, catalytic synthesis, oxygen reduction catalysis, drug sustained release, and electrochemical energy storage.

The technical scheme adopted in the present invention is:

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow core-shell structure, the preparation method comprising (1) or (1), (2) in the following steps:

Step (1): Prepare solid Cu ₂ O nanocrystalline particles or solid Au@Cu ₂ O core-shell nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution, Partial sulfurization of solid Cu ₂ O nanocrystals with controllable morphology in situ, or sulfurization of the Cu ₂ O shell in solid Au@Cu ₂ O core-shell nanocrystals, so that solid Cu ₂ O nanocrystals or Au@Cu ₂ O core-shell nanocrystals are transformed into Cu ₂ O/Cu ₂ S or Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure under the premise of maintaining the overall morphology in situ;

Step (2): For the Cu ₂ O/Cu ₂ S or Au/Cu ₂ S heterogeneous nanocrystalline particles with a hollow micro-reaction cavity structure, according to the chemical reactivity of the cation, the Cu ₂ S is externally layer into other sulfide semiconductors to obtain semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

Wherein, the solid Cu ₂ O nanocrystal particles are octahedral nanocrystal particles, cubic nanocrystal particles, octahedral cut corners, etc., and the vulcanization reaction is to combine the solid Cu ₂ O nanocrystals and solid Au@ Cu ₂ O core-shell nanocrystalline particles are dispersed in methanol aqueous solution, and then form a mixed solution with Na ₂ S aqueous solution with a concentration of 0.1 mol/L. After the mixed solution is stirred at 25°C for 10 seconds, the Centrifuge at a speed of 10 minutes for 10 minutes, and disperse the lower precipitate into methanol to obtain Cu ₂ O/Cu ₂ S or Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure.

The concentration of the Na ₂ S aqueous solution in the present invention is preferably 0.1mol/L, wherein every 10mL of solid Cu ₂ O nanocrystals or methanol sol of Au@Cu ₂ O core-shell nanocrystal particles is mixed with 0.01-0.5mL of Na ₂ S aqueous solutions are mixed. The S ^2- in the Na ₂ S aqueous solution described therein can undergo sulfuration reaction with Cu ₂ O, in situ partially sulfurize the solid Cu ₂ O nanocrystals with controllable morphology, or solidify the solid Au@Cu ₂ O The Cu ₂ O shell layer in the core-shell nanocrystals is vulcanized, and the solid Cu ₂ O nanocrystals or Au@Cu ₂ O core-shell nanocrystals are transformed into Cu ₂ O/Cu ₂ S or Au with a hollow micro-reaction cavity structure. /Cu ₂ S heterogeneous nanocrystals and maintain the original overall shape.

The step (2) of the present invention is based on the chemical reactivity of cations, using a controllable cation chemical reaction to convert the outer layer of Cu ₂ S into other sulfide semiconductors to obtain semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure .

As preferably, said step (2) includes the following steps:

Step 21, diluting the Cu ₂ O/Cu ₂ S or Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure with anhydrous methanol, and then mixing it with an aqueous metal salt solution to form a mixed liquid a;

Step 22, adding 60 μL of tributylphosphine to the mixed solution a to form a mixed solution b, and stirring the mixed solution b in a constant temperature water bath at 50-60°C for 120 minutes;

Step 23, after the stirring is completed, cool the mixed liquid b to 25°C, then centrifuge at 5000 rpm for 10 minutes, and disperse the obtained precipitate into anhydrous methanol to obtain a semiconductor substrate with a hollow micro-reaction chamber structure. heterogeneous nanocrystals.

Further preferably, the metal salt solution is a solution containing Cd ²⁺ , Zn ²⁺ or Sn ²⁺ .

In a preferred embodiment of the present invention, during the cationic chemical reaction, under the action of tributylphosphine, the Cu ₂ O/Cu ₂ S or Au/Cu ₂ S with a hollow micro-reaction chamber structure The outer layer of Cu ₂ S in heterogeneous nanocrystals undergoes cationic chemical reactions with other metal ions, while the Cu ₂ O core or Au does not undergo chemical reactions with other metal ions. Therefore, the Cu ₂ S outer layer in the Cu ₂ O/Cu ₂ S or Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure can be converted into other chalcogenide semiconductors by using the cationic chemical reaction step, It is preferably one of CdS, ZnS or SnS, and a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure is obtained.

The solid Cu ₂ O nanocrystals described in the present invention can be nanocrystals with any shape.

In a preferred embodiment of the present invention, the solid Cu ₂ O nanocrystals are solid Cu ₂ O octahedral nanocrystal particles, and its preparation includes the following steps:

Step 11, dissolving PVP, copper chloride, and sodium hydroxide in water to form a mixed solution c, and stirring at a constant temperature of 60° C. for 30 minutes;

Step 12, mixing the mixed solution c with an aqueous ascorbic acid solution to form a mixed solution d, stirring at a constant temperature at 60°C for 3 hours, and centrifuging at a speed of 5000 rpm for 10 minutes to obtain the solid Cu ₂ O octahedron nanocrystalline particles.

In another preferred embodiment of the present invention, the solid Cu ₂ O nanocrystalline particles are solid Cu ₂ O cubic nanocrystalline particles, and its preparation includes the following steps:

Dissolve PVP in water, then add copper nitrate aqueous solution, sodium hydroxide aqueous solution, and ascorbic acid aqueous solution successively to form a mixed solution e. Centrifuge at a rotational speed for 10 minutes to obtain the solid Cu ₂ O cubic nanocrystal particles.

The solid Au@Cu ₂ O core-shell nanocrystals described in the present invention can be prepared by any existing method. In another preferred embodiment of the present invention, the preparation of the solid Au@Cu ₂ O core-shell nanocrystals includes the following steps:

Step 31, preparation of Au nanoparticles;

Step 32: Mix and stir the Au nanoparticles and the PVP solution at 25°C, then add copper nitrate aqueous solution, sodium hydroxide aqueous solution, and ascorbic acid aqueous solution, the reaction solution rapidly changes from red to blue-green, and after stirring, the reaction solution turns to blue-green at 5000 rpm. Centrifuge at a speed of 10 minutes for 10 minutes to obtain solid Au@Cu ₂ O core-shell nanocrystalline particles.

The semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure prepared by the preparation method of the present invention is characterized in that the nano-core in the micro-cavity is Cu ₂ O or Au nanoparticles, and the outer layer material of the micro-cavity is The sulfide semiconductor is preferably one of CdS, ZnS, Cu ₂ S, and SnS.

Preferably, the particle size of the semiconductor-based heterogeneous nanocrystalline particles having a hollow micro-reaction cavity structure is 50-1000 nm, more preferably 100-250 nm.

Preferably, the semiconductor-based heterogeneous nanocrystalline particles having a hollow micro-reaction cavity structure have octahedral or cubic or arbitrary shapes.

The heterogeneous nanocrystal in the present invention is a composite nanocrystal structure formed by contacting two different components, and the semiconductor-based heterogeneous nanocrystal is a heterogeneous nanocrystal in which at least one component phase is a semiconductor.

The present invention provides a new method for preparing semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction chamber structure. Nanoparticles in the microcavity of semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction chamber structure prepared by the method The core is Cu ₂ O or Au particles, and the outer layer is sulfide semiconductor. The semiconductor-based heterogeneous nanocrystalline particles with a hollow micro-reaction cavity structure can have extensive research value in applications such as catalytic synthesis, sustained drug release, and electrochemical energy storage. Moreover, the preparation method of the present invention is simple to operate, has universal applicability in the preparation of semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure, and is of great significance for the synthesis of heterogeneous nanocrystals. Semiconductor-based heterogeneous nanocrystals with a hollow microreaction chamber structure provide an important basis and material basis. Mainly reflected in the following points:

(1) By using solid Cu ₂ O nanocrystalline particles and solid Au@Cu ₂ O core-shell nanocrystalline particles as raw materials, the vulcanization reaction is carried out, and the semiconductor substrate with a hollow micro-reaction cavity structure is obtained according to the anion diffusion rate. Heterogeneous nanocrystalline particles, and the formation of hollow micro-reaction chambers with different sizes through the regulation of anion diffusion rate, has brought new opportunities for the preparation and application of heterogeneous nanocrystals with new shapes.

(2) On the basis of obtaining semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure, the Cu ₂ S shell is converted into a variety of chalcogenide semiconductor shells, such as CdS, ZnS, and SnS, through cationic chemical reactions. The nanocrystals with hollow micro-reaction cavity structure provide a wider application in chemical reaction and selective catalysis. At the same time, this method provides a flexible and convenient synthetic route for the recombination of different components of semiconductor-based heterogeneous nanocrystals with hollow microreaction chamber structures.

(3) The prepared metal/semiconductor and metal oxide/semiconductor heterogeneous nanocrystals with a hollow micro-reaction cavity structure have controllable morphology and good crystallinity, and are suitable for photothermal conversion, photocatalytic degradation of dyes, and electrocatalytic oxygen reduction etc., have good application effects, and have good application prospects in catalytic organic synthesis, drug sustained release, electrochemical energy storage and so on. The size and shape of the hollow microcavity can be adjusted, so that the metal/semiconductor and metal oxide/semiconductor heterogeneous nanocrystals prepared by the method of the present invention have rich potential application value.

Description of drawings

₁ is a transmission electron microscope image of an octahedral Cu2O/Cu2S heterogeneous nanocrystal sample with a hollow micro _- reaction chamber structure prepared in Example 3 of the present invention;

Fig. ₂ is an X-ray powder diffraction pattern of an octahedral Cu2O/Cu2S heterogeneous nanocrystal sample with a hollow micro _- reaction chamber structure prepared in Example 3 of the present invention;

₃ is the light-to _- heat conversion curve of the octahedral Cu2O/Cu2S heterogeneous nanocrystal sample with a hollow micro-reaction chamber structure prepared in Example 3 of the present invention;

4 is a transmission electron microscope image of a cube _- shaped Cu2O/Cu2S heterogeneous nanocrystal sample with a hollow micro _- reaction chamber structure prepared in Example 4 of the present invention;

5 is a transmission electron microscope image of the Au/Cu ₂ S heterogeneous nanocrystal sample with a hollow micro-reaction chamber structure prepared in Example 5 of the present invention;

₆ is a transmission electron microscope picture of an octahedral Cu2O/CdS heterogeneous nanocrystal sample with a hollow micro-reaction chamber structure prepared in Example 6 of the present invention;

₇ is a transmission electron microscope picture of an octahedral Cu2O/ZnS heterogeneous nanocrystal sample with a hollow micro-reaction chamber structure prepared in Example 7 of the present invention;

Fig. ₈ is a transmission electron microscope picture of an octahedral Cu2O/SnS heterogeneous nanocrystal sample with a hollow micro-reaction chamber structure prepared in Example 8 of the present invention;

Fig. 9 is a transmission electron microscope picture of an Au/CdS heterogeneous nanocrystal sample with a hollow micro-reaction cavity structure prepared in Example 12 of the present invention;

FIG. 10 is a transmission electron microscope image of the Au/SnS heterogeneous nanocrystal sample with a hollow micro-reaction chamber structure prepared in Example 14 of the present invention.

detailed description

Other objects and advantages of the present invention will become clear by explaining the following preferred embodiments of the present application.

The reagents used in the following embodiments are as follows:

Sodium hydroxide (NaOH, 99%), ascorbic acid (99%), silver nitrate (AgNO ₃ , 99%), sodium sulfide (Na ₂ S, 99%), stannous chloride (SnCl ₂ 2H ₂ O, 99 %), methylene blue (AR) was purchased from Tianjin Guangfu Technology Development Co., Ltd.; polyvinylpyrrolidone (PVP, K30), chloroauric acid (HAuCl ₄ 4H ₂ O, 99%) was purchased from Sinopharm Group Chemical Co., Ltd.; cadmium nitrate ( Cd(NO ₃ ) ₂ 4H ₂ O, 99%), zinc nitrate (Zn(NO ₃ ) ₂ 6H ₂ O, 99%), tributylphosphine ((C ₄ H ₉ ) ₃ P, TBP, 99 %), purchased from Shanghai Crystal Pure Chemical Co., Ltd. (Aladdin); absolute ethanol (99%), anhydrous methanol (99%) acetonitrile (99%), and cyclohexane (99%) were purchased from Beijing Chemical Plant. All reagents were used without further purification. The above reagents are only the raw material reagents used to further illustrate the examples, and are not intended to further limit the scope of protection.

Example 1

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure, the preparation method comprising the following steps:

Prepare solid Cu ₂ O nanocrystalline particles or solid Au@Cu ₂ O core-shell nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution to in situ The solid Cu ₂ O nanocrystals with controlled morphology are partially vulcanized, or the Cu ₂ O shell in the solid Au@Cu ₂ O core-shell nanocrystals is vulcanized, so that the solid Cu ₂ O nanocrystals or Au@Cu ₂ O The core-shell nanocrystals are transformed into Cu ₂ O/Cu ₂ S or Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure under the premise of maintaining the overall morphology in situ.

Example 2

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction chamber structure, the preparation method comprising (1) and (2) in the following steps:

Step (1): Prepare solid Cu ₂ O nanocrystalline particles or solid Au@Cu ₂ O core-shell nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution, Partial sulfurization of solid Cu ₂ O nanocrystals with controllable morphology in situ, or sulfurization of the Cu ₂ O shell in solid Au@Cu ₂ O core-shell nanocrystals, so that solid Cu ₂ O nanocrystals or Au@Cu ₂ O core-shell nanocrystals are transformed into Cu ₂ O/Cu ₂ S or Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure under the premise of maintaining the overall morphology in situ;

Step (2): For the Cu ₂ O/Cu ₂ S or Au/Cu ₂ S heterogeneous nanocrystalline particles with a hollow micro-reaction cavity structure, according to the chemical reactivity of the cations, the Cu ₂ S is externally layer into other sulfide semiconductors to obtain semiconductor-based heterogeneous nanocrystals with hollow microreaction cavity structures.

Example 3

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure, comprising the steps of:

Step (1): Prepare solid Cu ₂ O nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution to in situ form solid Cu ₂ O particles with controllable morphology O nanocrystals are partially vulcanized to obtain Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure.

The solid Cu ₂ O nanocrystalline particles with controllable morphology in this embodiment are solid Cu ₂ O octahedral nanocrystalline particles, and their preparation includes the following steps:

Dissolve PVP (4.44g) in water (50mL), add copper chloride solution (1mol/L, 0.3mL) and sodium hydroxide solution (10mol/L, 0.3mL) to form solution c, keep the temperature at 60°C for 30 minutes . The mixed solution c was mixed with ascorbic acid (1mol/L, 3mL) to form a mixed solution d, stirred at 60°C for 3 hours, then centrifuged at 5000 rpm for 10 minutes to obtain the solid Cu ₂ O The nano-octahedral crystal particles were dispersed in anhydrous methanol (5 mL) to obtain a solid Cu ₂ O nano-octahedral crystal particle sol.

Take the solid Cu ₂ O nano-octahedral crystal particle sol (1 mL) prepared above, add 0.050 mL of Na ₂ S aqueous solution (0.1 mol/L) to form a mixed solution and stir for 10 seconds. Centrifuge at a rotating speed for 10 minutes to obtain octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure, which are dispersed in anhydrous methanol (5 mL).

The octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment were detected by a transmission electron microscope and an X-ray powder diffractometer, and the results are shown in Figure 1 and Figure 2 . It can be seen from Figure 1 that the Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure synthesized by the preparation method described in Example 1 are octahedral, and the Cu ₂ O core inside the cavity There is a gap between Cu ₂ S and the outer layer, which also shows that the prepared product is indeed a structure with a hollow micro-reaction cavity. It can also be seen from the XRD pattern of Figure 2 that the product prepared by the preparation method described in Example 1 is composed of Cu ₂ O and Cu ₂ S, and has good crystallinity, which proves that the product prepared in Example 1 is hollow Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with micro-reaction cavity structure.

Take a certain amount of octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure prepared in this example and place them in a transparent quartz cuvette, add 1 mL of deionized water, and mix well When irradiated with a laser with a wavelength of 808nm and a power of 0.5W, the temperature in the water rises rapidly, indicating that the octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this example have remarkable optical properties. The heat conversion effect and the light-to-heat conversion curve are shown in Figure 3.

Example 4

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure, comprising the steps of:

Step (1): Prepare solid Cu ₂ O nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution to in situ form solid Cu ₂ O particles with controllable morphology O nanocrystals are partially vulcanized to obtain Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure.

The solid Cu ₂ O nanocrystalline particles with controllable morphology in this embodiment are solid Cu ₂ O cubic nanocrystalline particles, and the preparation thereof includes the following steps:

Dissolve PVP (4.44g) in water (50mL), add copper chloride solution (1mol/L, 0.3mL), sodium hydroxide solution (10mol/L, 1mL), ascorbic acid solution (1mol/L, 1mL). The solution turns from blue to green and yellow, and then gradually produces a yellow precipitate to form a suspension. After stirring at room temperature for 3 hours, centrifuge at 5000 rpm for 10 minutes to obtain the solid Cu ₂ O cubic nanocrystal particles, and redisperse them in anhydrous methanol (5 mL) to obtain solid Cu ₂ O cubes Nanocrystalline particle sol.

Take the solid Cu ₂ O cubic nanocrystalline particle sol (1 mL) prepared above, add 0.050 mL of Na ₂ S aqueous solution (0.1 mol/L) to form a mixed solution, stir for 10 seconds, and then Centrifuge for 10 minutes. Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure were obtained and dispersed into anhydrous methanol (5 mL).

The cube-shaped Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment were detected by a transmission electron microscope, as shown in Figure 4

Example 5:

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure, comprising the steps of:

Step (1): Prepare solid Au@Cu ₂ O core-shell nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution to in situ The solid Au@Cu ₂ O core-shell nanocrystals were partially vulcanized to obtain Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure.

The solid Cu ₂ O nanocrystalline particles with controllable morphology in this example are solid Au@Cu ₂ O core-shell nanocrystalline particles, and their preparation includes the following steps:

Step 31, the preparation of Au nanoparticles, specifically:

Chlorauric acid solution (5mg/mL, 0.8mL) was added to water (80mL) at 80°C and reduced with sodium citrate solution (1%, 0.8mL) to obtain Au nanoparticle sol.

Step 32, take the Au nanoparticle sol (10mL), add PVP solution (1%, 3mL) and stir at 25°C, add copper nitrate solution (10mmol/L, 20μL), sodium hydroxide solution (1mol/L, 1mL ), ascorbic acid solution (1mol/L, 1mL), the reaction solution rapidly changed from red to blue-green. After stirring for 10 min, centrifuge at 5000 rpm for 10 min to obtain solid Au@Cu2O core _- shell nanocrystalline particles, which were dispersed in water (10 mL) to obtain solid Au@Cu2O core _- shell Nanocrystalline particle sol.

Take the solid Au@Cu ₂ O core-shell nanocrystalline particle sol (1 mL) prepared above, add 0.050 mL of Na ₂ S aqueous solution (0.1 mol/L) to form a mixed solution and stir it for 10 seconds at 5000 rpm Centrifuge at a rotation speed of 10 minutes to obtain Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure, which are dispersed in anhydrous methanol (5 mL).

The Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment were detected by a transmission electron microscope, as shown in FIG. 5 . The Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment have uniform morphology and good monodispersity, and have a significant catalytic effect as a catalyst in the electrocatalytic oxygen reduction reaction.

Example 6

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure, comprising the steps of:

Step (1): Prepare solid Cu ₂ O nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution to in situ form solid Cu ₂ O particles with controllable morphology O nanocrystals are partially vulcanized to obtain Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure.

The solid Cu ₂ O nanocrystalline particles with controllable morphology in this embodiment are solid Cu ₂ O octahedral nanocrystalline particles, and their preparation includes the following steps:

Dissolve PVP (4.44g) in water (50mL), add copper chloride solution (1mol/L, 0.3mL) and sodium hydroxide solution (10mol/L, 0.3mL) to form solution c, keep the temperature at 60°C for 30 minutes . The mixed solution c was mixed with ascorbic acid (1mol/L, 3mL) to form a mixed solution d, stirred at 60°C for 3 hours, then centrifuged at 5000 rpm for 10 minutes to obtain the solid Cu ₂ O The nano-octahedral crystal particles were dispersed in anhydrous methanol (5 mL) to obtain a solid Cu ₂ O nano-octahedral crystal particle sol.

Take the solid Cu ₂ O nano-octahedral crystal particle sol (1 mL) prepared above, add 0.050 mL of Na ₂ S aqueous solution (0.1 mol/L) to form a mixed solution and stir for 10 seconds. Centrifuge at high speed for 10 minutes. Octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure were obtained, dispersed in anhydrous methanol (5 mL), and octahedral Cu ₂ O/Cu 2 S with a hollow micro-reaction chamber structure was obtained. Cu ₂ S heterogeneous nanocrystalline particle sol.

Step (2): For the Cu ₂ O/Cu ₂ S heterogeneous nanocrystalline particles with a hollow micro-reaction cavity structure, according to the chemical reactivity of the cations, the outer layer of Cu ₂ S is converted into other sulfides by a cationic chemical reaction Semiconductor, obtaining semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

The semiconductor-based heterogeneous nanocrystalline particles with a hollow micro _- reaction chamber structure in this embodiment are octahedral Cu2O/CdS heterogeneous nanocrystal particles with a hollow micro-reaction chamber structure, and its preparation includes the following steps:

Step 21, take the octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystalline sol (1 mL) with a hollow micro-reaction cavity structure prepared in the above step (1), dilute it to 15 mL with anhydrous methanol, add metal salts, In this embodiment, it is cadmium nitrate (30mg/mL, 1mL), forming a mixed solution a;

Step 22, place the above mixed solution a in a water bath at 60°C to keep the temperature constant, add TBP (50 μL) to form mixed solution b, and continue to stir for 30 minutes. During the reaction process, the color of the nanocrystalline sol gradually changed from brown to yellow;

Step 23, after the stirring is completed, the mixed solution b is cooled to 25°C, and then centrifuged at a speed of 5000 rpm for 10 minutes, and the obtained lower layer precipitate is dispersed in anhydrous methanol to obtain an octahedral hollow cell. Cu ₂ O/CdS heterogeneous nanocrystalline sol with reaction chamber structure.

The octahedral Cu ₂ O/CdS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment were detected by a transmission electron microscope, as shown in FIG. 6 .

Example 7

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure, comprising the steps of:

Step (1): Prepare solid Cu ₂ O nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution to in situ form solid Cu ₂ O particles with controllable morphology O nanocrystals are partially vulcanized to obtain Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

The solid Cu ₂ O nanocrystalline particles with controllable morphology in this embodiment are solid Cu ₂ O octahedral nanocrystalline particles, and their preparation includes the following steps:

Dissolve PVP (4.44g) in water (50mL), add copper chloride solution (1mol/L, 0.3mL) and sodium hydroxide solution (10mol/L, 0.3mL) to form solution c, keep the temperature at 60°C for 30 minutes . The mixed solution c was mixed with ascorbic acid (1mol/L, 3mL) to form a mixed solution d, stirred at 60°C for 3 hours, then centrifuged at 5000 rpm for 10 minutes to obtain the solid Cu ₂ O Nano-octahedral crystal particles were dispersed in anhydrous methanol (5 mL) to obtain a solid Cu ₂ O nano-octahedral crystal particle sol.

Take the solid Cu ₂ O nano-octahedral crystal particle sol (1 mL) prepared above, add 0.050 mL of Na ₂ S aqueous solution (0.1 mol/L) to form a mixed solution and stir for 10 seconds. Centrifuge at high speed for 10 minutes. Octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure were obtained, dispersed in anhydrous methanol (5 mL), and octahedral Cu ₂ O/Cu 2 S with a hollow micro-reaction chamber structure was obtained. Cu ₂ S heterogeneous nanocrystalline particle sol.

Step (2): For the Cu ₂ O/Cu ₂ S heterogeneous nanocrystalline particles with a hollow micro-reaction cavity structure, according to the chemical reactivity of the cations, the outer layer of Cu ₂ S is converted into other sulfides by a cationic chemical reaction Semiconductor, obtaining semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

The semiconductor-based heterogeneous nanocrystalline particles with a hollow micro _- reaction chamber structure in this embodiment are octahedral Cu2O/ZnS heterogeneous nanocrystal particles with a hollow micro-reaction chamber structure, and its preparation includes the following steps:

Step 21, take the octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystalline sol (1 mL) with a hollow micro-reaction cavity structure prepared in the above step (1), dilute it to 15 mL with anhydrous methanol, add metal salts, In this embodiment, zinc nitrate (30mg/mL, 1mL) forms a mixed solution a;

Step 22, place the above mixed solution a in a water bath at 60°C to keep the temperature constant, add TBP (50 μL) to form mixed solution b, and continue to stir for 30 minutes. During the reaction process, the color of the nanocrystalline sol gradually changed from brown to yellow;

Step 23, after the stirring is completed, the mixed solution b is cooled to 25°C, and then centrifuged at a speed of 5000 rpm for 10 minutes, and the obtained lower layer precipitate is dispersed in anhydrous methanol to obtain an octahedral hollow cell. Cu ₂ O/ZnS heterogeneous nanocrystalline sol with reaction chamber structure.

The octahedral Cu ₂ O/ZnS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment were detected by a transmission electron microscope, as shown in FIG. 7 . The octahedral Cu ₂ O/ZnS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment have potential application value in the field of photocatalysis.

Example 8

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure, comprising the steps of:

Step (1): Prepare solid Cu ₂ O nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution to in situ form solid Cu ₂ O particles with controllable morphology O nanocrystals are partially vulcanized to obtain Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

The solid Cu ₂ O nanocrystalline particles with controllable morphology in this embodiment are solid Cu ₂ O octahedral nanocrystalline particles, and their preparation includes the following steps:

Dissolve PVP (4.44g) in water (50mL), add copper chloride solution (1mol/L, 0.3mL) and sodium hydroxide solution (10mol/L, 0.3mL) to form solution c, keep the temperature at 60°C for 30 minutes . The mixed solution c was mixed with ascorbic acid (1mol/L, 3mL) to form a mixed solution d, stirred at 60°C for 3 hours, then centrifuged at 5000 rpm for 10 minutes to obtain the solid Cu ₂ O The nano-octahedral crystal particles were dispersed in anhydrous methanol (5 mL) to obtain a solid Cu ₂ O nano-octahedral crystal particle sol.

Take the solid Cu ₂ O nano-octahedral crystal particle sol (1 mL) prepared above, add 0.050 mL of Na ₂ S aqueous solution (0.1 mol/L) to form a mixed solution and stir for 10 seconds. Centrifuge at high speed for 10 minutes. Octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure were obtained, dispersed in anhydrous methanol (5 mL), and octahedral Cu ₂ O/Cu 2 S with a hollow micro-reaction chamber structure was obtained. Cu ₂ S heterogeneous nanocrystalline sol.

Step (2): For the Cu ₂ O/Cu ₂ S heterogeneous nanocrystalline particles with a hollow micro-reaction cavity structure, according to the chemical reactivity of the cations, the outer layer of Cu ₂ S is converted into other sulfides by a cationic chemical reaction Semiconductor, obtaining semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

The semiconductor-based heterogeneous nanocrystalline particles with a hollow micro _- reaction chamber structure in this embodiment are octahedral Cu2O/SnS heterogeneous nanocrystal particles with a hollow micro-reaction chamber structure, and its preparation includes the following steps:

Step 21, take the octahedral Cu ₂ O/Cu ₂ S heterogeneous nanocrystalline sol (1 mL) with a hollow micro-reaction cavity structure prepared in the above step (1), dilute it to 15 mL with anhydrous methanol, add metal salts, In the present embodiment, it is stannous chloride (30mg/mL, 1mL), forming mixed solution a;

Step 22, place the above mixed solution a in a water bath at 60°C to keep the temperature constant, add TBP (50 μL) to form mixed solution b, and continue to stir for 30 minutes. During the reaction process, the color of the nanocrystalline sol gradually changed from brown to yellow;

Step 23, after the stirring is completed, the mixed solution b is cooled to 25°C, and then centrifuged at a speed of 5000 rpm for 10 minutes, and the obtained lower layer precipitate is dispersed in anhydrous methanol to obtain an octahedral hollow cell. Cu ₂ O/SnS heterogeneous nanocrystalline sol with reaction chamber structure.

The octahedral Cu ₂ O/SnS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment were detected by a transmission electron microscope, as shown in FIG. 8 . Place the above-prepared octahedral Cu ₂ O/SnS heterogeneous nanocrystalline sol with a hollow micro-reaction cavity structure in a transparent quartz cuvette, add a certain amount of methylene blue aqueous solution, and use a Xe lamp with a power of 300W. When irradiated in visible light mode, the absorbance of the solution decreases rapidly (the color becomes lighter rapidly), which shows that the octahedral Cu ₂ O/SnS heterogeneous nanocrystals with hollow micro-reaction cavity structure prepared in this embodiment are effective in the photocatalytic degradation of methylene blue. In the reaction, it has a significant catalytic effect.

Example 9

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure, comprising the steps of:

Step (1): Prepare solid Cu ₂ O nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution to in situ form solid Cu ₂ O particles with controllable morphology O nanocrystals are partially vulcanized to obtain Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

The solid Cu ₂ O nanocrystalline particles with controllable morphology in this embodiment are solid Cu ₂ O cubic nanocrystalline particles, and the preparation thereof includes the following steps:

Dissolve PVP (4.44g) in water (50mL), add copper chloride solution (1mol/L, 0.3mL), sodium hydroxide solution (10mol/L, 1mL), ascorbic acid solution (1mol/L, 1mL). The solution turns from blue to green and yellow, and then gradually produces a yellow precipitate to form a suspension. After stirring at room temperature for 3 hours, it was centrifuged at 5000 rpm for 10 minutes. The obtained solid Cu ₂ O cubic nanocrystal particles were redispersed in anhydrous methanol (5 mL) to obtain a solid Cu ₂ O cubic nanocrystal particle sol.

Take the solid Cu ₂ O cubic nanocrystalline particle sol (1 mL) prepared above, add 0.050 mL of Na ₂ S aqueous solution (0.1 mol/L) to form a mixed solution, stir for 10 seconds, and then Centrifuge for 10 minutes. Obtain cube-shaped Cu ₂ O/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure, disperse them in anhydrous methanol (5mL), and obtain a cube-shaped Cu ₂ O/Cu with a hollow micro-reaction chamber structure ₂ S heterogeneous nanocrystalline particle sol.

Step (2): For the Cu ₂ O/Cu ₂ S heterogeneous nanocrystalline particles with a hollow micro-reaction cavity structure, according to the chemical reactivity of the cations, the outer layer of Cu ₂ S is converted into other sulfides by a cationic chemical reaction Semiconductor, obtaining semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

The semiconductor-based heterogeneous nanocrystalline particles with a hollow micro-reaction chamber structure in this embodiment are cube _- shaped Cu2O/CdS heterogeneous nanocrystal particles with a hollow micro-reaction chamber structure, and its preparation includes the following steps:

Step 21, take the cube-shaped Cu ₂ O/Cu ₂ S heterogeneous nanocrystalline sol (1 mL) prepared in the above step (1) with a hollow micro-reaction cavity structure, dilute it to 15 mL with anhydrous methanol, and add metal salts. In the embodiment, it is cadmium nitrate (30mg/mL, 1mL), forming a mixed solution a;

Step 22, place the above mixed solution a in a water bath at 60°C to keep the temperature constant, add TBP (50 μL) to form mixed solution b, and continue to stir for 30 minutes. During the reaction process, the color of the nanocrystalline sol gradually changed from brown to yellow;

Step 23, after the stirring is completed, cool the mixed liquid b to 25°C, then centrifuge at a speed of 5000 rpm for 10 minutes, and disperse the obtained lower precipitate into anhydrous methanol to obtain a cube-shaped hollow microreaction Cu ₂ O/CdS heterogeneous nanocrystalline sol with cavity structure.

The cube-shaped Cu ₂ O/CdS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment have potential application value in the field of photocatalysis.

Example 10

Same as Example 9, except that the metal salt used in step (2) is zinc nitrate, and finally a cube-shaped Cu ₂ O/ZnS heterogeneous nanocrystalline sol with a hollow micro-reaction cavity structure is obtained. The cube-shaped Cu ₂ O/ZnS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment have potential application value in the field of photocatalysis.

Example 11

The same as Example 9, except that the metal salt used in step (2) is stannous chloride, and finally a cube-shaped Cu ₂ O/SnS heterogeneous nanocrystalline sol with a hollow micro-reaction cavity structure is obtained. The cube-shaped Cu ₂ O/SnS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment have potential application value in the field of photocatalytic degradation of dyes.

Example 12

A method for preparing a semiconductor-based heterogeneous nanocrystal with a hollow micro-reaction cavity structure, comprising the steps of:

Step (1): Prepare solid Au@Cu ₂ O core-shell nanocrystalline particles with controllable morphology, and use a certain concentration of Na ₂ S aqueous solution in methanol aqueous solution to in situ Solid Au@Cu ₂ O core-shell nanocrystals are partially vulcanized to obtain Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

The preparation of solid Au@Cu ₂ O core-shell nanocrystalline particles in this example includes the following steps:

Step 31, the preparation of Au nanoparticles, specifically:

Chlorauric acid solution (5mg/mL, 0.8mL) was added to water (80mL) at 80°C and reduced with sodium citrate solution (1%, 0.8mL) to obtain Au nanoparticle sol.

Step 32, take the Au nanoparticle sol (10mL), add PVP solution (1%, 3mL) and stir at 25°C, add copper nitrate solution (10mmol/L, 20μL), sodium hydroxide solution (1mol/L, 1mL ), ascorbic acid solution (1mol/L, 1mL), the reaction solution rapidly changed from red to blue-green. After stirring for 10 min, centrifuge at 5000 rpm for 10 min to obtain solid Au@Cu2O core _- shell nanocrystalline particles, which were dispersed in water (10 mL) to obtain solid Au@Cu2O core _- shell Nanocrystalline particle sol.

Take the solid Au@Cu ₂ O core-shell nanocrystalline particle sol (1 mL) prepared above, add 0.050 mL of Na ₂ S aqueous solution (0.1 mol/L) to form a mixed solution, stir for 10 seconds, and then Centrifuge at a speed of 10 minutes for 10 minutes to obtain Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure, and disperse them in anhydrous methanol (5 mL) to obtain Au/Cu ₂ S heterogeneous nanocrystals with a hollow micro-reaction chamber structure. Nanocrystalline particle sol.

Step (2): For the Au/Cu ₂ S heterogeneous nanocrystalline particles with a hollow micro-reaction cavity structure, according to the chemical reactivity of cations, the outer layer of Cu ₂ S is converted into other sulfide semiconductors by chemical reaction of cations, Obtain semiconductor-based heterogeneous nanocrystals with a hollow micro-reaction cavity structure;

The semiconductor-based heterogeneous nanocrystalline particles with a hollow micro-reaction chamber structure in this embodiment are Au/CdS heterogeneous nanocrystalline particles with a hollow micro-reaction chamber structure, and its preparation includes the following steps:

Step 21, take the Au/Cu ₂ S heterogeneous nanocrystalline particle sol (1mL) with a hollow micro-reaction chamber structure prepared in the above step (1), dilute it to 15mL with anhydrous methanol, and add a metal salt, which is Cadmium nitrate (30mg/mL, 1mL) to form a mixed solution a;

Step 22, place the above mixed solution a in a water bath at 60°C to keep the temperature constant, add TBP (50 μL) to form mixed solution b, and continue to stir for 30 minutes. During the reaction process, the color of the nanocrystalline sol gradually changed from brown to blue or purple;

Step 23, after the stirring is completed, the mixed liquid b is cooled to 25°C, and then centrifuged at a speed of 5000 rpm for 10 minutes, and the obtained lower precipitate is dispersed into anhydrous methanol to obtain a hollow micro-reaction cavity structure Au/CdS heterogeneous nanocrystalline sol.

The Au/CdS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment were detected by a transmission electron microscope, as shown in FIG. 9 . The Au/CdS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment have potential application value in the field of photocatalytic hydrogen production.

Example 13

The same as in Example 12, except that the metal salt used in step (2) is zinc nitrate, and an Au/ZnS heterogeneous nanocrystalline sol with a hollow micro-reaction cavity structure is finally obtained. The Au/ZnS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment have potential application value in the field of photocatalytic hydrogen production.

Example 14

The same as Example 12, except that the metal salt used in step (2) is stannous chloride, and finally obtains an Au/SnS heterogeneous nanocrystalline sol with a hollow micro-reaction cavity structure. The Au/SnS heterogeneous nanocrystals with a hollow micro-reaction chamber structure prepared in this embodiment were detected by a transmission electron microscope, as shown in FIG. 10 . Put the Au/SnS heterogeneous nanocrystalline sol with a hollow micro-reaction chamber structure in a transparent quartz cuvette, add a certain amount of methylene blue aqueous solution, use a Xe lamp with a power of 300W, and irradiate it under visible light mode, the absorbance of the solution is rapid decrease (the color becomes lighter rapidly), indicating that the Au/SnS heterogeneous nanocrystals with a hollow micro-reaction cavity structure prepared in this embodiment have a significant catalytic effect in the photocatalytic degradation of methylene blue.

Claims (10)

1. a kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, the preparation method include (1) or (1), (2) in following steps：

Step (1)：Prepare the solid Cu with controllable appearance₂O nano-crystalline granules or solid Au@Cu₂Brilliant of O core-shell nanos Grain, and distribute it in the aqueous solution of the methanol of certain volume, by adding certain density Na₂The S aqueous solution, in a constant temperature It is degree lower stirring certain time, in situ by the solid Cu with controllable appearance₂The nanocrystalline partial vulcanizations of O, or by solid Au@ Cu₂Cu in O core-shell nano crystalline substances₂O shells vulcanize, and make solid Cu₂O is nanocrystalline or Au@Cu₂O core-shell nanos are brilliant, and original position is simultaneously protected On the premise of holding overall pattern, it is changed into the Cu with hollow reaction microchamber structure₂O/Cu₂S or Au/Cu₂S hetero-nanocrystals；

Step (2)：To the Cu with hollow reaction microchamber structure₂O/Cu₂S or Au/Cu₂S hetero-nanocrystals particles, according to The chemical reactivity of cation, reacted using cationic chemical by Cu₂S outer layers are converted into other sulfide semiconductors, obtain Semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure；

Wherein, the solid Cu₂O nanocrystalline can be arbitrary shape looks, and subordinate is solid Cu₂O octahedrons nano-crystalline granule or Solid Cu₂O cube nano-crystalline granules, the vulcanization reaction are by the solid Cu₂Au@Cu nanocrystalline or solid O₂O Core-shell nano crystalline substance particle is distributed in methanol aqueous solution, then the Na with concentration for 0.1mol/L₂The S aqueous solution forms mixed liquor, After the mixed liquor is stirred 10 seconds at 25 DEG C, centrifugal concentrating 10 minutes under 5000 revs/min of rotating speed, will be precipitated immediately It is distributed in absolute methanol, obtains the Cu with hollow reaction microchamber structure₂O/Cu₂S or Au/Cu₂S hetero-nanocrystals particles are molten Glue.

2. preparation method according to claim 1, it is characterised in that：The step (2) comprises the following steps：

Step 21, by the Cu with hollow reaction microchamber structure₂O/Cu₂S or Au/Cu₂S hetero-nanocrystals absolute methanols Dilution, is then mixed with aqueous metal salt, forms mixed liquor a；

Step 22,60 μ L tributylphosphine is added into the mixed liquor a, forms mixed liquor b, and the mixed liquor b is placed in Stirred 120 minutes in 50-60 DEG C of water bath with thermostatic control；

Step 23, the mixed liquor b is cooled to 25 DEG C after stirring terminates, then centrifuges 10 under 5000 revs/min of rotating speed Minute, obtained lower sediment is dispersed in absolute methanol, obtains that there is the semiconductor-based heterogeneous of hollow reaction microchamber structure It is nanocrystalline.

3. according to the preparation method described in claim any one of 1-2, it is characterised in that：The Na₂The concentration of the S aqueous solution is 0.1mol/L, wherein per Cu solid 10ml₂O nano-crystalline granules or solid Au@Cu₂The methanol sol of O core-shell nano crystalline substance particles With 0.01-0.5ml Na₂The S aqueous solution is mixed, after mixed liquor quickly stirs 10 seconds at 25 DEG C, immediately 5000 Rev/min rotating speed under centrifuge 10 minutes, precipitation is distributed in absolute methanol, obtained with hollow reaction microchamber structure Cu₂O/Cu₂S or Au/Cu₂S hetero-nanocrystals particle colloidal sols.

4. preparation method according to claim 1 or 2, the solid Cu of the controllable appearance₂O nano-crystalline granules are solid Cu₂O octahedron nano-crystalline granules, its preparation comprise the following steps：

Step 11, PVP, copper chloride, sodium hydroxide are dissolved in the water to form mixed liquor c, 60 DEG C of constant temperature stir 30 minutes；

Step 12, the mixed liquor c is mixed with aqueous ascorbic acid, forms mixed solution d, 60 DEG C of constant temperature stir 3 hours Afterwards, centrifuged 10 minutes under 5000 revs/min of rotating speed, obtain the solid Cu₂O octahedron nano-crystalline granules.

5. preparation method according to claim 1 or 2, it is characterised in that the solid Cu of the controllable appearance₂O is nanocrystalline Particle is solid Cu₂O cube nano-crystalline granules, its preparation comprise the following steps：

PVP is dissolved in the water, then sequentially adds copper nitrate aqueous solution, sodium hydrate aqueous solution, aqueous ascorbic acid, shape Into mixed solution e, at room temperature, after the mixed solution e is stirred, centrifuge 10 minutes, obtain under 5000 revs/min of rotating speed To described solid Cu₂O cube nano-crystalline granules.

6. preparation method according to claim 1, it is characterised in that the solid Au@Cu₂The brilliant preparation bag of O core-shell nanos Include following steps：

Step 31, the preparation of Au nano particles；

Step 32, the Au nano particles are mixed and stirred at 25 DEG C with PVP solution, add copper nitrate aqueous solution, hydrogen Aqueous solution of sodium oxide, aqueous ascorbic acid, reaction solution are changed into blue-green by red rapidly, at 5000 revs/min after stirring Rotating speed under centrifuge 10 minutes, obtain solid Au@Cu₂O core-shell nano crystalline substance particles.

7. there is the semiconductor-based different of hollow reaction microchamber structure as prepared by the preparation method described in claim any one of 1-6 Matter is nanocrystalline, it is characterised in that the nanometer core wherein in microcavity is Cu₂O or Au nano particles, the cladding material shell of microcavity are Chalcogen semiconductor.

8. the semiconductor-based hetero-nanocrystals according to claim 7 with hollow reaction microchamber structure, it is characterised in that The cladding material of the microcavity is CdS, ZnS, Cu₂S, one kind in SnS.

9. the semiconductor-based hetero-nanocrystals according to claim 7 with hollow reaction microchamber structure, it is characterised in that The particle diameter of the described semiconductor-based hetero-nanocrystals particle with hollow reaction microchamber structure is 100-250nm.

10. the semiconductor-based hetero-nanocrystals according to claim 7 with hollow reaction microchamber structure, its feature exist In the described semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure are octahedra or cube structure.