CN106629815B - A kind of semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure and preparation method thereof - Google Patents
A kind of semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure and preparation method thereof.Utilize Na2S aqueous solution original position is by solid Cu2Nanocrystalline partial vulcanizations of O or by solid Au@Cu2The brilliant Cu of O core-shell nanos2O shells vulcanize, and make solid Cu2O is nanocrystalline or Au@Cu2O core-shell nanos are brilliant, are changed into the Cu with hollow reaction microchamber structure2O/Cu2S or Au/Cu2S hetero-nanocrystals and pattern holding；Cationoid reaction is recycled by Cu2S outer layers are converted into other chalcogen semiconductors, obtain the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, wherein microcavity kernel is Cu2O or Au are nanocrystalline, and outer layer is sulfide semiconductor, preferably CdS, ZnS, Cu2S、SnS.The inventive method is simple, and kernel and cladding material composition, pattern is adjustable, is that heterocatalysis, catalysis organic synthesis, medicament slow release etc. provide reaction microchamber.
Description
Technical field
The present invention relates to the nanocrystalline material of novel nano pattern and control synthesis field, more particularly to heterojunction structure is received
A kind of rice crystalline material, and in particular to semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure and preparation method thereof；
The nanocrystalline material can be applied to the fields such as photothermal deformation, photocatalytic degradation of dye.
Background technology
With the nanocrystalline of hollow reaction microchamber structure, it is a kind of critically important nano crystal material, can be urged for out-phase
Change, be catalyzed the reaction microchamber that the offers such as organic synthesis, medicament slow release, electrochemical cell chemically react, and then in these sides
Face has a wide range of applications, be current nano material it is synthetically prepared in hot subject.First, there is hollow reaction microchamber knot
The nanocrystalline application in terms of catalysis of structure is very extensive, is such as used for photothermal deformation, photocatalytic degradation of dye, photocatalytic synthesis into,
Selective catalytic oxidation or reduction, lithium ion battery electrode material, sodium ion battery electrode material, Thermosensitive Material Used for Controlled Releasing of Medicine etc..Closely
Nian Lai, due between the kernel and outer layer of such a structure there is cavity can be used as microreactor, many new catalyst quilts
Such a structure is designed as to improve the selectivity of catalytic reaction.Such nanocrystalline hollow reaction microchamber structure can also be by setting
Count the means such as the duct size of its shell so that only moieties or reaction intermediate can enter micro-nano reactor so as to
Improve the selectivity of reaction, the design of the catalyst of this structure and synthesis have also attracted that vast catalytic chemistry worker's is emerging
Interest.
In studying at this stage, nanocrystalline method of the synthesis with hollow reaction microchamber structure is mainly directly in hollow knot
Structure grows or by being modified outer layer or being handled to be formed being formed on the basis of core shell structure, another common synthesis
Method is by introducing intermediate layer during core shell structure is built, and is removed finally by the means mode such as thermal decomposition or corrosion
Intermediate layer is so as to forming reaction microchamber.The preparation process of these methods is very cumbersome, and the nanocrystal being prepared does not possess
Good crystallinity, the serious nanocrystalline application for restricting the hollow reaction microchamber structure obtained.Especially report at present this
The nanocrystalline mainly oxide/oxide of class, metal/oxide hetero-nanocrystals, more types of metal/semiconductor, oxygen
Compound/semiconductor structure it is nanocrystalline very deficient, but these combination caused by have hollow reaction microchamber structure semiconductor
Base hetero-nanocrystals have very big potential in application aspects such as catalysis, energy storage, different performance coupling, surface plasma bulk effects
Application value.Therefore how a kind of new, general, gold of the preparation with hollow reaction microchamber structure of universality is provided
Category/semiconductor, the nanocrystalline method of metal oxide/heterogeneous semiconductor, there is critically important application value.
The content of the invention
The defects of existing for prior art, the invention provides a kind of semiconductor-based with hollow reaction microchamber structure
Hetero-nanocrystals (including metal/semiconductor, metal oxide/semiconductor combinations) and its universality preparation method, this method behaviour
Make it is simple, and can by regulating and controlling preparation condition, obtain various combination, reaction microchamber structure it is adjustable there is hollow micro- reaction
The semiconductor-based hetero-nanocrystals of cavity configuration.
The invention provides a kind of side of new semiconductor-based hetero-nanocrystals of the preparation with hollow reaction microchamber structure
Method, this method can have general applicability in such Syntheses field, be prepared using preparation method of the present invention
The obtained semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure can photocatalytic degradation of dye, catalyze and synthesize,
The fields such as hydrogen reduction catalysis, medicament slow release, electrochemical energy storage are with a wide range of applications.
The technical solution adopted by the present invention is：
A kind of preparation method of the semiconductor-based hetero-nanocrystals of hollow core shell structure, the preparation method include following step
(1) or (1), (2) in rapid：
Step (1)：Prepare the solid Cu with controllable appearance2O nano-crystalline granules or solid Au@Cu2O core-shell nanos
Brilliant particle, and in the aqueous solution of methanol, utilize certain density Na2The S aqueous solution, original position is by with the solid of controllable appearance
Cu2The nanocrystalline partial vulcanizations of O, or by solid Au@Cu2Cu in O core-shell nano crystalline substances2O shells vulcanize, and make solid Cu2O
Nanocrystalline or Au@Cu2O core-shell nanos are brilliant, in situ and on the premise of keeping overall pattern, are changed into hollow reaction microchamber knot
The Cu of 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 the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure；
Wherein, the solid Cu2O nano-crystalline granules are octahedra nano-crystalline granule, cube nano-crystalline granule, corner cut
Octahedron etc., the vulcanization reaction are by the solid Cu2Au@Cu nanocrystalline and solid O2O core-shell nano crystalline substance particles disperse
Into methanol aqueous solution, then with concentration be 0.1mol/L Na2The S aqueous solution forms mixed liquor, by the mixed liquor at 25 DEG C
After lower stirring 10 seconds, centrifuged 10 minutes under 5000 revs/min of rotating speed immediately, lower sediment is distributed in methanol, obtained
Cu with hollow reaction microchamber structure2O/Cu2S or Au/Cu2S hetero-nanocrystals.
Na of the present invention2The concentration of the S aqueous solution is preferably 0.1mol/L, wherein per Cu solid 10mL2O it is nanocrystalline or
Au@Cu2The methanol sol of O core-shell nano crystalline substance particles and 0.01-0.5mL Na2The S aqueous solution is mixed.It is wherein described
Na2S in the S aqueous solution2-Can and Cu2O carries out vulcanization reaction, in situ by the solid Cu with controllable appearance2The nanocrystalline portions of O
Point vulcanization, or by solid Au@Cu2Cu in O core-shell nano crystalline substances2O shells vulcanize, by solid Cu2O is nanocrystalline or Au@
Cu2O core-shell nanos are brilliant, are changed into the Cu with hollow reaction microchamber structure2O/Cu2S or Au/Cu2S hetero-nanocrystals are simultaneously kept
Originally overall pattern.
Step (2) of the present invention is the chemical reactivity according to cation, is reacted using controllable cationic chemical
By Cu2S outer layers are converted into other sulfide semiconductors, obtain the semiconductor-based heterogeneous nanometer with hollow reaction microchamber structure
It is brilliant.
Preferably, the step (2) comprises the following steps：
Step 21, by the Cu with hollow reaction microchamber structure2O/Cu2S or Au/Cu2S hetero-nanocrystals are with anhydrous
Methanol dilution, then mixed with aqueous metal salt, form mixed liquor a；
Step 22, add 60 μ L tributylphosphine into the mixed liquor a, form mixed liquor b, and by the mixed liquor b
It is placed in 50-60 DEG C of water bath with thermostatic control and stirs 120 minutes；
Step 23, the mixed liquor b is cooled to 25 DEG C after stirring terminates, then centrifuged under 5000 revs/min of rotating speeds
10 minutes, obtained precipitation is dispersed in absolute methanol, obtains having the semiconductor-based of hollow reaction microchamber structure heterogeneous to receive
Meter Jing.
It is further preferred that described metal salt solution is to contain Cd2+、Zn2+Or Sn2+Solution.
In a preferred embodiment of the invention, in the cationic chemical course of reaction, in the work of tributylphosphine
Under, the Cu with hollow reaction microchamber structure2O/Cu2S or Au/Cu2Cu in S hetero-nanocrystals2S outer layers and other
Metal ion occurs cationic chemical and reacted, and Cu2O cores or Au are not present to be showed with what other metal ions chemically reacted
As.Therefore can be by the Cu with hollow reaction microchamber structure using the cationic chemical reactions steps2O/Cu2S or
Au/Cu2Cu in S hetero-nanocrystals2S outer layers are converted into other chalcogen semiconductors, preferably one kind in CdS, ZnS or SnS,
Obtain the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure.
Solid Cu of the present invention2O nanocrystals can be the nanocrystal of arbitrary shape looks.
In a preferred embodiment of the invention, solid Cu2O nanocrystals are solid Cu2O octahedrons are nanocrystalline
Particle, 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 stirrings 3
After hour, centrifuged 10 minutes under 5000 revs/min of rotating speed, obtain described solid Cu2O octahedron nano-crystalline granules.
In another preferred embodiment of the invention, the solid Cu2O nano-crystalline granules are solid Cu2O cubes
Body nano-crystalline granule, its preparation comprise the following steps：
PVP is dissolved in the water, then sequentially adds copper nitrate aqueous solution, sodium hydrate aqueous solution, ascorbic acid is water-soluble
Liquid, mixed solution e is formed, at room temperature, the mixed solution e is stirred, after forming lemon yellow precipitation, at 5000 revs/min
Centrifuged 10 minutes under the rotating speed of clock, obtain described solid Cu2O cube nano-crystalline granules.
Solid Au@Cu of the present invention2O core-shell nanos crystalline substance can use any existing method to prepare.In this hair
In another bright preferred embodiment, the solid Au@Cu2The brilliant preparation of O core-shell nanos comprises the 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, it is water-soluble adds copper nitrate
Liquid, sodium hydrate aqueous solution, aqueous ascorbic acid, reaction solution are changed into blue-green by red rapidly, after stirring 5000 turns/
Centrifuged 10 minutes under the rotating speed of minute, obtain solid Au@Cu2O core-shell nano crystalline substance particles.
Semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure prepared by preparation method of the present invention, its
It is characterised by, the nanometer core wherein in microcavity is Cu2O or Au nano particles, the cladding material of microcavity is sulfide semiconductor, excellent
Elect CdS, ZnS, Cu as2S, one kind in SnS.
Preferably, the particle diameter of the described semiconductor-based hetero-nanocrystals particle with hollow reaction microchamber structure is 50-
1000nm, more preferably 100-250nm.
Preferably, the semiconductor-based hetero-nanocrystals particle with hollow reaction microchamber structure for it is octahedra or cube
Body or any pattern.
Hetero-nanocrystals of the present invention are in contact the composite nanocrystal structure formed by two kinds of different compositions,
Described semiconductor-based hetero-nanocrystals are at least one into the hetero-nanocrystals that split-phase is semiconductor.
The invention provides a kind of side of new semiconductor-based hetero-nanocrystals of the preparation with hollow reaction microchamber structure
Method, utilize the nanometer core in the microcavity of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure prepared by this method
For Cu2O or Au particles, outer layer are sulfide semiconductor.The semiconductor-based heterogeneous nanometer with hollow reaction microchamber structure
Brilliant particle can catalyze and synthesize, the application aspect such as medicament slow release, electrochemical energy storage has extensive researching value.And the present invention
Described preparation method is simple to operate, with general on the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure are prepared
Time applicability, to synthesis hetero-nanocrystals it is significant, for synthesize with specific morphology with hollow reaction microchamber
The semiconductor-based hetero-nanocrystals of structure provide important evidence and material foundation.Be mainly reflected in it is following some：
(1) by with solid Cu2O nano-crystalline granules and solid Au@Cu2O core-shell nano crystalline substances particle is raw material, is carried out
Vulcanization reaction, it is different according to the diffusion rate of anion, obtain the semiconductor-based heterogeneous nanometer with hollow reaction microchamber structure
Brilliant particle, and there are different dimension hollow reaction microchambers by the regulation and control formation to anion diffusion rate, to prepare new shape
The hetero-nanocrystals of looks and application bring new opportunity.
(2) on the basis of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure are obtained, cation is passed through
Chemically react Cu2S shells are converted into a variety of chalcogen semiconductor shells, such as CdS, ZnS, SnS, and this is hollow reaction microchamber knot
Structure nanocrystal is chemically reacting and is providing more wide application in selective catalysis.Meanwhile this method is hollow micro- anti-
The compound of the different component of the semiconductor-based hetero-nanocrystals of cavity configuration is answered to provide a kind of flexible, convenient route of synthesis.
(3) metal/semiconductor with hollow reaction microchamber structure being prepared, metal oxide/heterogeneous semiconductor
Nanocrystalline, morphology controllable, crystallinity is good, in photothermal deformation, photocatalytic degradation of dye, electrocatalytic oxidation reduction etc., has very
Good application effect, and have good application prospect in catalysis organic synthesis, medicament slow release, electrochemical energy storage etc..In
The size and shape adjustability of empty microcavity so that the metal with hollow reaction microchamber structure that the inventive method is prepared/
Semiconductor, metal oxide/heterogeneous semiconductor is nanocrystalline to possess abundant potential using value.
Brief description of the drawings
Fig. 1 is the Cu with hollow reaction microchamber structure of the octahedral shape prepared by the embodiment of the present invention 32O/Cu2S is different
The transmission electron micrograph of the nanocrystalline sample of matter；
Fig. 2 is the Cu with hollow reaction microchamber structure of the octahedral shape prepared by the embodiment of the present invention 32O/Cu2S is different
The X-ray powder diffraction pattern of the nanocrystalline sample of matter；
Fig. 3 is the Cu with hollow reaction microchamber structure of the octahedral shape prepared by the embodiment of the present invention 32O/Cu2S is different
The photothermal deformation curve of the nanocrystalline sample of matter；
Fig. 4 is the Cu with hollow reaction microchamber structure of the cubic prepared by the embodiment of the present invention 42O/Cu2S is different
The transmission electron micrograph of the nanocrystalline sample of matter；
Fig. 5 is the Au/Cu with hollow reaction microchamber structure prepared by the embodiment of the present invention 52S hetero-nanocrystals samples
Transmission electron micrograph；
Fig. 6 is the Cu with hollow reaction microchamber structure of the octahedral shape prepared by the embodiment of the present invention 62O/CdS is different
The transmission electron micrograph of the nanocrystalline sample of matter；
Fig. 7 is the Cu with hollow reaction microchamber structure of the octahedral shape prepared by the embodiment of the present invention 72O/ZnS is different
The transmission electron micrograph of the nanocrystalline sample of matter；
Fig. 8 is the Cu with hollow reaction microchamber structure of the octahedral shape prepared by the embodiment of the present invention 82O/SnS is different
The transmission electron micrograph of the nanocrystalline sample of matter；
Fig. 9 is the Au/CdS hetero-nanocrystals samples with hollow reaction microchamber structure prepared by the embodiment of the present invention 12
Transmission electron micrograph；
Figure 10 is the Au/SnS hetero-nanocrystals samples with hollow reaction microchamber structure prepared by the embodiment of the present invention 14
The transmission electron micrograph of product.
Embodiment
By explaining the preferred embodiment of following the application, other objects of the present invention and advantage will be clear.
Reagent used in implementation below is as described below：
Sodium hydroxide (NaOH, 99%), ascorbic acid (99%), silver nitrate (AgNO3, 99%), vulcanized sodium (Na2S,
99%), stannous chloride (SnCl2·2H2O, 99%), methylene blue (AR) is bought in Tianjin recovery development in science and technology Co., Ltd；It is poly-
Vinylpyrrolidone (PVP, K30), gold chloride (HAuCl4·4H2O, 99%) buy in Chinese medicines group Chemical Co., Ltd.；Nitric acid
Cadmium (Cd (NO3)2·4H2O, 99%), zinc nitrate (Zn (NO3)2·6H2O, 99%), tributylphosphine ((C4H9)3P, TBP, 99%),
Buy in Shanghai crystalline substance pure chemistry Co., Ltd (Aladdin)；Absolute ethyl alcohol (99%), absolute methanol (99%) acetonitrile (99%),
Hexamethylene (99%) is bought in Beijing Chemical Plant.All reagents are not purified further before use.Above reagent is only
The raw materials used reagent of embodiment is further illustrated, is not intended as the further restriction to protection domain.
Embodiment 1
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, the preparation method bag
Include following steps：
Prepare the solid Cu with controllable appearance2O nano-crystalline granules or solid Au@Cu2O core-shell nano crystalline substance particles, and
In the aqueous solution of methanol, certain density Na is utilized2The S aqueous solution, it is in situ by the solid Cu with controllable appearance2O is nanocrystalline
Partial vulcanization, 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, in situ and on the premise of keeping overall pattern, are changed into the Cu with hollow reaction microchamber structure2O/
Cu2S or Au/Cu2S hetero-nanocrystals.
Embodiment 2
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, the preparation method bag
Include (1), (2) in following steps：
Step (1)：Prepare the solid Cu with controllable appearance2O nano-crystalline granules or solid Au@Cu2O core-shell nanos
Brilliant particle, and in the aqueous solution of methanol, utilize certain density Na2The S aqueous solution, original position is by with the solid of controllable appearance
Cu2The nanocrystalline partial vulcanizations of O, or by solid Au@Cu2Cu in O core-shell nano crystalline substances2O shells vulcanize, and make solid Cu2O
Nanocrystalline or Au@Cu2O core-shell nanos are brilliant, in situ and on the premise of keeping overall pattern, are changed into hollow reaction microchamber knot
The Cu of 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 the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure.
Embodiment 3
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, comprises the following steps：
Step (1)：Prepare the solid Cu with controllable appearance2O nano-crystalline granules, and in the aqueous solution of methanol, profit
With certain density Na2The S aqueous solution, it is in situ by the solid Cu with controllable appearance2The nanocrystalline partial vulcanizations of O, in being had
The Cu of empty reaction microchamber structure2O/Cu2S hetero-nanocrystals.
The solid Cu of controllable appearance in the present embodiment2O nano-crystalline granules are solid Cu2O is octahedra nanocrystalline
Grain, its preparation comprise the following steps：
PVP (4.44g) is dissolved in water (50mL), adds copper chloride solution (1mol/L, 0.3mL), sodium hydroxide is molten
Liquid (10mol/L, 0.3mL), forms solution c, 60 DEG C of constant temperature 30 minutes.By the mixed liquor c and ascorbic acid (1mol/L,
3mL) mix, form mixed solution d, after 60 DEG C of constant temperature stir 3 hours, centrifuge 10 minutes, obtain under 5000 revs/min of rotating speed
Obtain the solid Cu2O nanometer octahedral crystal particles, are distributed in absolute methanol (5mL), obtain solid Cu2O nanometers eight
Face body crystal grain colloidal sol.
Take the solid Cu of above-mentioned preparation2O nanometer octahedral crystal particle colloidal sols (1mL), add 0.050mL Na2S's
The aqueous solution (0.1mol/L), after forming mixed liquor stirring 10 seconds, centrifuge 10 minutes, obtain under 5000 revs/min of rotating speed
The Cu with hollow reaction microchamber structure of octahedral shape2O/Cu2S hetero-nanocrystals, it is dispersed in absolute methanol (5mL).
The Cu with hollow reaction microchamber structure for the octahedral shape that present embodiment is prepared2O/Cu2S is heterogeneous to be received
Meter Jing is detected by transmission electron microscope and x-ray powder diffraction instrument, as a result such as Fig. 1, shown in Fig. 2.Can from Fig. 1
Go out, the Cu with hollow reaction microchamber structure synthesized using the preparation method described in embodiment 12O/Cu2S hetero-nanocrystals are
Octahedral shape, and the Cu in cavity2The Cu of O kernels and outer layer2There is gap, this also illustrates the product of preparation is true between S
Actually there is the structure of hollow reaction microchamber.As Fig. 2 XRD spectrum it can also be seen that prepared by the preparation method described in embodiment 1
Product by Cu2O and Cu2S is formed, and crystallinity is good, and what these all demonstrated that embodiment 1 prepares is with hollow micro- anti-
Answer the Cu of cavity configuration2O/Cu2S hetero-nanocrystals.
Take the Cu with hollow reaction microchamber structure of a certain amount of octahedral shape manufactured in the present embodiment2O/Cu2S is heterogeneous
It is nanocrystalline to be placed in transparent quartz colorimetric utensil, 1mL deionized waters are added, the use of wavelength are 808nm after being well mixed, power is
0.5W laser irradiates, and temperature rises rapidly in water, and illustrate octahedral shape manufactured in the present embodiment has hollow reaction microchamber
The Cu of structure2O/Cu2S hetero-nanocrystals have a significant photothermal deformation effect, and photothermal deformation curve is as shown in Figure 3.
Embodiment 4
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, comprises the following steps：
Step (1)：Prepare the solid Cu with controllable appearance2O nano-crystalline granules, and in the aqueous solution of methanol, profit
With certain density Na2The S aqueous solution, it is in situ by the solid Cu with controllable appearance2The nanocrystalline partial vulcanizations of O, in being had
The Cu of empty reaction microchamber structure2O/Cu2S hetero-nanocrystals.
The solid Cu of controllable appearance in the present embodiment2O nano-crystalline granules are solid Cu2Nanocrystalline of O cubes
Grain, its preparation comprise the following steps：
PVP (4.44g) is dissolved in water (50mL), adds copper chloride solution (1mol/L, 0.3mL), sodium hydroxide is molten
Liquid (10mol/L, 1mL), ascorbic acid solution (1mol/L, 1mL).Solution is changed into green by blueness, and yellow is rear gradually to produce
Yellow mercury oxide, form suspension.After stirring 3 hours at room temperature, centrifuged 10 minutes under 5000 revs/min of rotating speed, obtain institute
State solid Cu2O cube nano-crystalline granules, it is dispersed to again in absolute methanol (5mL), obtains solid Cu2O cubes are received
The brilliant particle colloidal sols of rice.
Take the solid Cu of above-mentioned preparation2O cube nano-crystalline granule colloidal sols (1mL), add 0.050mL Na2S water
Solution (0.1mol/L), after forming mixed liquor stirring 10 seconds, centrifuged 10 minutes under 5000 revs/min of rotating speed.Had
There is the Cu of hollow reaction microchamber structure2O/Cu2S hetero-nanocrystals, it is dispersed in absolute methanol (5mL).
The Cu with hollow reaction microchamber structure for the cubic that present embodiment is prepared2O/Cu2S is heterogeneous to be received
Meter Jing is detected by transmission electron microscope, as shown in Figure 4
Embodiment 5：
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, comprises the following steps：
Step (1)：Prepare the solid Au@Cu with controllable appearance2O core-shell nano crystalline substance particles, and in the water-soluble of methanol
In liquid, certain density Na is utilized2The S aqueous solution, it is in situ by the solid Au@Cu with controllable appearance2O core-shell nano crystalline substances part
Vulcanization, obtains the Au/Cu with hollow reaction microchamber structure2S hetero-nanocrystals.
The solid Cu of controllable appearance in the present embodiment2O nano-crystalline granules are solid Au@Cu2Brilliant of O core-shell nanos
Grain, its preparation comprise the following steps：
Step 31, the preparation of Au nano particles, it is specially：
Chlorauric acid solution (5mg/mL, 0.8mL) is added in 80 DEG C of water (80mL), and uses sodium citrate solution
(1%, 0.8mL) is reduced, and obtains Au nano particle colloidal sols.
Step 32, the Au nano particles colloidal sol (10mL) is taken, adds at 25 DEG C of PVP solution (1%, 3mL) and stirs, is added
Copper nitrate solution (10mmol/L, 20 μ L), sodium hydroxide solution (1mol/L, 1mL), ascorbic acid solution (1mol/L, 1mL),
Reaction solution is changed into blue-green by red rapidly.After stirring 10 minutes, centrifuge 10 minutes, obtain under 5000 revs/min of rotating speed
To solid Au@Cu2O core-shell nano crystalline substance particles, and be distributed in water (10mL), obtain solid Au@Cu2Brilliant of O core-shell nanos
Grain colloidal sol.
Take the solid Au@Cu of above-mentioned preparation2O core-shell nano crystalline substance particle colloidal sols (1mL), add 0.050mL Na2S water
Solution (0.1mol/L), formed after mixed liquor stirs 10 seconds and centrifuged 10 minutes under 5000 revs/min of rotating speed, had
The Au/Cu of hollow reaction microchamber structure2S hetero-nanocrystals, it is dispersed in absolute methanol (5mL).
The Au/Cu with hollow reaction microchamber structure that present embodiment is prepared2S hetero-nanocrystals pass through transmission
Electron microscope is detected, as shown in Figure 5.Au/Cu with hollow reaction microchamber structure prepared by present embodiment2S is different
Matter is nanocrystalline, and pattern is homogeneous, and monodispersity is good, there is significant catalysis effect in electrocatalytic oxidation reduction reaction as catalyst
Fruit.
Embodiment 6
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, comprises the following steps：
Step (1)：Prepare the solid Cu with controllable appearance2O nano-crystalline granules, and in the aqueous solution of methanol, profit
With certain density Na2The S aqueous solution, it is in situ by the solid Cu with controllable appearance2The nanocrystalline partial vulcanizations of O, in being had
The Cu of empty reaction microchamber structure2O/Cu2S hetero-nanocrystals.
The solid Cu of controllable appearance in the present embodiment2O nano-crystalline granules are solid Cu2O is octahedra nanocrystalline
Grain, its preparation comprise the following steps：
PVP (4.44g) is dissolved in water (50mL), adds copper chloride solution (1mol/L, 0.3mL), sodium hydroxide is molten
Liquid (10mol/L, 0.3mL), forms solution c, 60 DEG C of constant temperature 30 minutes.By the mixed liquor c and ascorbic acid (1mol/L,
3mL) mix, form mixed solution d, after 60 DEG C of constant temperature stir 3 hours, centrifuge 10 minutes, obtain under 5000 revs/min of rotating speed
Obtain the solid Cu2O nanometer octahedral crystal particles, are distributed in absolute methanol (5mL), obtain solid Cu2O nanometers eight
Face body crystal grain colloidal sol.
Take the solid Cu of above-mentioned preparation2O nanometer octahedral crystal particle colloidal sols (1mL), add 0.050mL Na2S's
The aqueous solution (0.1mol/L), after forming mixed liquor stirring 10 seconds, centrifuged 10 minutes under 5000 revs/min of rotating speed.Obtain
The Cu with hollow reaction microchamber structure of octahedral shape2O/Cu2S hetero-nanocrystals, it is dispersed in absolute methanol (5mL), obtains
The Cu with hollow reaction microchamber structure of octahedral shape2O/Cu2S hetero-nanocrystals particle colloidal sols.
Step (2)：To the Cu with hollow reaction microchamber structure2O/Cu2S hetero-nanocrystals particles, according to cation
Chemical reactivity, using cationic chemical reaction by Cu2S outer layers are converted into other sulfide semiconductors, in being had
The semiconductor-based hetero-nanocrystals of empty reaction microchamber structure；
The semiconductor-based hetero-nanocrystals particle with hollow reaction microchamber structure in the present embodiment is octahedral shape
Cu with hollow reaction microchamber structure2O/CdS hetero-nanocrystals particles, its preparation comprise the following steps：
Step 21, the Cu with hollow reaction microchamber structure of the octahedral shape of above-mentioned steps (1) preparation is taken2O/Cu2S is different
Matter nanocrystalline colloidal sol (1mL), 15mL is diluted to absolute methanol, adds metal salt, in the present embodiment for cadmium nitrate (30mg/mL,
1mL), mixed liquor a is formed；
Step 22, above-mentioned mixed liquor a is positioned over constant temperature in 60 DEG C of water-baths, adds TBP (50 μ L), form mixed solution b,
And continue stirring 30 minutes.In course of reaction, the color of nanocrystalline colloidal sol is gradually changed into yellow by brown；
Step 23, the mixed liquor b is cooled to 25 DEG C by stirring after terminating, then under 5000 revs/min of rotating speed from
The heart 10 minutes, obtained lower sediment is dispersed in absolute methanol, and obtain octahedral shape has hollow reaction microchamber structure
Cu2O/CdS hetero-nanocrystals colloidal sols.
The Cu with hollow reaction microchamber structure for the octahedral shape that present embodiment is prepared2O/CdS is heterogeneous to be received
Meter Jing is detected by transmission electron microscope, as shown in Figure 6.
Embodiment 7
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, comprises the following steps：
Step (1)：Prepare the solid Cu with controllable appearance2O nano-crystalline granules, and in the aqueous solution of methanol, profit
With certain density Na2The S aqueous solution, it is in situ by the solid Cu with controllable appearance2The nanocrystalline partial vulcanizations of O, in being had
The Cu of empty reaction microchamber structure2O/Cu2S hetero-nanocrystals；
The solid Cu of controllable appearance in the present embodiment2O nano-crystalline granules are solid Cu2O is octahedra nanocrystalline
Grain, its preparation comprise the following steps：
PVP (4.44g) is dissolved in water (50mL), adds copper chloride solution (1mol/L, 0.3mL), sodium hydroxide is molten
Liquid (10mol/L, 0.3mL), forms solution c, 60 DEG C of constant temperature 30 minutes.By the mixed liquor c and ascorbic acid (1mol/L,
3mL) mix, form mixed solution d, after 60 DEG C of constant temperature stir 3 hours, centrifuge 10 minutes, obtain under 5000 revs/min of rotating speed
Obtain the solid Cu2O nanometer octahedral crystal particles, are distributed in absolute methanol (5mL), obtain solid Cu2O nanometers eight
Face body crystalline substance particle colloidal sols.
Take the solid Cu of above-mentioned preparation2O nanometer octahedral crystal particle colloidal sols (1mL), add 0.050mL Na2S's
The aqueous solution (0.1mol/L), after forming mixed liquor stirring 10 seconds, centrifuged 10 minutes under 5000 revs/min of rotating speed.Obtain
The Cu with hollow reaction microchamber structure of octahedral shape2O/Cu2S hetero-nanocrystals, it is dispersed in absolute methanol (5mL), obtains
The Cu with hollow reaction microchamber structure of octahedral shape2O/Cu2S hetero-nanocrystals particle colloidal sols.
Step (2)：To the Cu with hollow reaction microchamber structure2O/Cu2S hetero-nanocrystals particles, according to cation
Chemical reactivity, using cationic chemical reaction by Cu2S outer layers are converted into other sulfide semiconductors, in being had
The semiconductor-based hetero-nanocrystals of empty reaction microchamber structure；
The semiconductor-based hetero-nanocrystals particle with hollow reaction microchamber structure in the present embodiment is octahedral shape
Cu with hollow reaction microchamber structure2O/ZnS hetero-nanocrystals particles, its preparation comprise the following steps：
Step 21, the Cu with hollow reaction microchamber structure of the octahedral shape of above-mentioned steps (1) preparation is taken2O/Cu2S is different
Matter nanocrystalline colloidal sol (1mL), 15mL is diluted to absolute methanol, adds metal salt, in the present embodiment for zinc nitrate (30mg/mL,
1mL), mixed liquor a is formed；
Step 22, above-mentioned mixed liquor a is positioned over constant temperature in 60 DEG C of water-baths, adds TBP (50 μ L), form mixed solution b,
And continue stirring 30 minutes.In course of reaction, the color of nanocrystalline colloidal sol is gradually changed into yellow by brown；
Step 23, the mixed liquor b is cooled to 25 DEG C by stirring after terminating, then under 5000 revs/min of rotating speed from
The heart 10 minutes, obtained lower sediment is dispersed in absolute methanol, and obtain octahedral shape has hollow reaction microchamber structure
Cu2O/ZnS hetero-nanocrystals colloidal sols.
The Cu with hollow reaction microchamber structure for the octahedral shape that present embodiment is prepared2O/ZnS is heterogeneous to be received
Meter Jing is detected by transmission electron microscope, as shown in Figure 7.In the having of the octahedral shape that present embodiment is prepared
The Cu of empty reaction microchamber structure2O/ZnS hetero-nanocrystals have potential application value in photocatalysis field.
Embodiment 8
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, comprises the following steps：
Step (1)：Prepare the solid Cu with controllable appearance2O nano-crystalline granules, and in the aqueous solution of methanol, profit
With certain density Na2The S aqueous solution, it is in situ by the solid Cu with controllable appearance2The nanocrystalline partial vulcanizations of O, in being had
The Cu of empty reaction microchamber structure2O/Cu2S hetero-nanocrystals；
The solid Cu of controllable appearance in the present embodiment2O nano-crystalline granules are solid Cu2O is octahedra nanocrystalline
Grain, its preparation comprise the following steps：
PVP (4.44g) is dissolved in water (50mL), adds copper chloride solution (1mol/L, 0.3mL), sodium hydroxide is molten
Liquid (10mol/L, 0.3mL), forms solution c, 60 DEG C of constant temperature 30 minutes.By the mixed liquor c and ascorbic acid (1mol/L,
3mL) mix, form mixed solution d, after 60 DEG C of constant temperature stir 3 hours, centrifuge 10 minutes, obtain under 5000 revs/min of rotating speed
Obtain the solid Cu2O nanometer octahedral crystal particles, are distributed in absolute methanol (5mL), obtain solid Cu2O nanometers eight
Face body crystal grain colloidal sol.
Take the solid Cu of above-mentioned preparation2O nanometer octahedral crystal particle colloidal sols (1mL), add 0.050mL Na2S's
The aqueous solution (0.1mol/L), after forming mixed liquor stirring 10 seconds, centrifuged 10 minutes under 5000 revs/min of rotating speed.Obtain
The Cu with hollow reaction microchamber structure of octahedral shape2O/Cu2S hetero-nanocrystals, it is dispersed in absolute methanol (5mL), obtains
The Cu with hollow reaction microchamber structure of octahedral shape2O/Cu2S hetero-nanocrystals colloidal sols.
Step (2)：To the Cu with hollow reaction microchamber structure2O/Cu2S hetero-nanocrystals particles, according to cation
Chemical reactivity, using cationic chemical reaction by Cu2S outer layers are converted into other sulfide semiconductors, in being had
The semiconductor-based hetero-nanocrystals of empty reaction microchamber structure；
The semiconductor-based hetero-nanocrystals particle with hollow reaction microchamber structure in the present embodiment is octahedral shape
Cu with hollow reaction microchamber structure2O/SnS hetero-nanocrystals particles, its preparation comprise the following steps：
Step 21, the Cu with hollow reaction microchamber structure of the octahedral shape of above-mentioned steps (1) preparation is taken2O/Cu2S is different
Matter nanocrystalline colloidal sol (1mL), 15mL is diluted to absolute methanol, adds metal salt, be stannous chloride (30mg/ in the present embodiment
ML, 1mL), form mixed liquor a；
Step 22, above-mentioned mixed liquor a is positioned over constant temperature in 60 DEG C of water-baths, adds TBP (50 μ L), form mixed solution b,
And continue stirring 30 minutes.In course of reaction, the color of nanocrystalline colloidal sol is gradually changed into yellow by brown；
Step 23, the mixed liquor b is cooled to 25 DEG C by stirring after terminating, then under 5000 revs/min of rotating speed from
The heart 10 minutes, obtained lower sediment is dispersed in absolute methanol, and obtain octahedral shape has hollow reaction microchamber structure
Cu2O/SnS hetero-nanocrystals colloidal sols.
The Cu with hollow reaction microchamber structure for the octahedral shape that present embodiment is prepared2O/SnS is heterogeneous to be received
Meter Jing is detected by transmission electron microscope, as shown in Figure 8.The octahedral shape of above-mentioned preparation had into hollow micro- reaction
The Cu of cavity configuration2O/SnS hetero-nanocrystals colloidal sols are placed in transparent quartz colorimetric utensil, and it is water-soluble to add a certain amount of methylene blue
Liquid, using the Xe lamps that power is 300W, being irradiated under visible mode, solution absorbance declines rapidly (color shoals rapidly),
Illustrate the Cu with hollow reaction microchamber structure for the octahedral shape that present embodiment is prepared2O/SnS hetero-nanocrystals exist
In the reaction of photocatalytic degradation methylene blue, there is significant catalytic effect.
Embodiment 9
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, comprises the following steps：
Step (1)：Prepare the solid Cu with controllable appearance2O nano-crystalline granules, and in the aqueous solution of methanol, profit
With certain density Na2The S aqueous solution, it is in situ by the solid Cu with controllable appearance2The nanocrystalline partial vulcanizations of O, in being had
The Cu of empty reaction microchamber structure2O/Cu2S hetero-nanocrystals；
The solid Cu of controllable appearance in the present embodiment2O nano-crystalline granules are solid Cu2Nanocrystalline of O cubes
Grain, its preparation comprise the following steps：
PVP (4.44g) is dissolved in water (50mL), adds copper chloride solution (1mol/L, 0.3mL), sodium hydroxide is molten
Liquid (10mol/L, 1mL), ascorbic acid solution (1mol/L, 1mL).Solution is changed into green by blueness, and yellow is rear gradually to produce
Yellow mercury oxide, form suspension.After stirring 3 hours at room temperature, centrifuged 10 minutes under 5000 revs/min of rotating speed.Obtain
Solid Cu2O cube nano-crystalline granules, it is dispersed to again in absolute methanol (5mL), obtains solid Cu2O cube nanometers
Brilliant particle colloidal sols.
Take the solid Cu of above-mentioned preparation2O cube nano-crystalline granule colloidal sols (1mL), add 0.050mL Na2S water
Solution (0.1mol/L), after forming mixed liquor stirring 10 seconds, centrifuged 10 minutes under 5000 revs/min of rotating speed.Stood
The Cu with hollow reaction microchamber structure of cube shape2O/Cu2S hetero-nanocrystals, it is dispersed in absolute methanol (5mL), is stood
The Cu with hollow reaction microchamber structure of cube shape2O/Cu2S hetero-nanocrystals particle colloidal sols.
Step (2)：To the Cu with hollow reaction microchamber structure2O/Cu2S hetero-nanocrystals particles, according to cation
Chemical reactivity, using cationic chemical reaction by Cu2S outer layers are converted into other sulfide semiconductors, in being had
The semiconductor-based hetero-nanocrystals of empty reaction microchamber structure；
The semiconductor-based hetero-nanocrystals particle with hollow reaction microchamber structure in the present embodiment is cubic
Cu with hollow reaction microchamber structure2O/CdS hetero-nanocrystals particles, its preparation comprise the following steps：
Step 21, the Cu with hollow reaction microchamber structure of the cubic of above-mentioned steps (1) preparation is taken2O/Cu2S is different
Matter nanocrystalline colloidal sol (1mL), 15mL is diluted to absolute methanol, adds metal salt, in the present embodiment for cadmium nitrate (30mg/mL,
1mL), mixed liquor a is formed；
Step 22, above-mentioned mixed liquor a is positioned over constant temperature in 60 DEG C of water-baths, adds TBP (50 μ L), form mixed solution b,
And continue stirring 30 minutes.In course of reaction, the color of nanocrystalline colloidal sol is gradually changed into yellow by brown；
Step 23, the mixed liquor b is cooled to 25 DEG C by stirring after terminating, then under 5000 revs/min of rotating speed from
The heart 10 minutes, obtained lower sediment is dispersed in absolute methanol, and obtain cubic has hollow reaction microchamber structure
Cu2O/CdS hetero-nanocrystals colloidal sols.
The Cu with hollow reaction microchamber structure of cubic made from present embodiment2O/CdS hetero-nanocrystals exist
Photocatalysis field has potential application value.
Embodiment 10
With embodiment 9, difference is in step (2) that metal salt used is zinc nitrate, finally gives cubic
Cu with hollow reaction microchamber structure2O/ZnS hetero-nanocrystals colloidal sols.In the having of cubic made from present embodiment
The Cu of empty reaction microchamber structure2O/ZnS hetero-nanocrystals have potential application value in photocatalysis field.
Embodiment 11
With embodiment 9, difference is in step (2) that metal salt used is stannous chloride, finally gives cubic
The Cu with hollow reaction microchamber structure2O/SnS hetero-nanocrystals colloidal sols.Cubic made from present embodiment has
The Cu of hollow reaction microchamber structure2O/SnS hetero-nanocrystals have potential application value in photocatalytic degradation of dye field.
Embodiment 12
A kind of preparation method of the semiconductor-based hetero-nanocrystals with hollow reaction microchamber structure, comprises the following steps：
Step (1)：Prepare the solid Au@Cu with controllable appearance2O core-shell nano crystalline substance particles, and in the water-soluble of methanol
In liquid, certain density Na is utilized2The S aqueous solution, it is in situ by the solid Au@Cu with controllable appearance2O core-shell nano crystalline substances part
Vulcanization, obtains the Au/Cu with hollow reaction microchamber structure2S hetero-nanocrystals；
Solid Au@Cu in the present embodiment2O core-shell nano crystalline substance particles, its preparation comprise the following steps：
Step 31, the preparation of Au nano particles, it is specially：
Chlorauric acid solution (5mg/mL, 0.8mL) is added in 80 DEG C of water (80mL), and uses sodium citrate solution
(1%, 0.8mL) is reduced, and obtains Au nano particle colloidal sols.
Step 32, the Au nano particles colloidal sol (10mL) is taken, adds at 25 DEG C of PVP solution (1%, 3mL) and stirs, is added
Copper nitrate solution (10mmol/L, 20 μ L), sodium hydroxide solution (1mol/L, 1mL), ascorbic acid solution (1mol/L, 1mL),
Reaction solution is changed into blue-green by red rapidly.After stirring 10 minutes, centrifuge 10 minutes, obtain under 5000 revs/min of rotating speed
To solid Au@Cu2O core-shell nano crystalline substance particles, and be distributed in water (10mL), obtain solid Au@Cu2Brilliant of O core-shell nanos
Grain colloidal sol.
Take the solid Au@Cu of above-mentioned preparation2O core-shell nano crystalline substance particle colloidal sols (1mL), add 0.050mL Na2S water
Solution (0.1mol/L), after forming mixed liquor stirring 10 seconds, centrifuge 10 minutes, had under 5000 revs/min of rotating speed
There is the Au/Cu of hollow reaction microchamber structure2S hetero-nanocrystals, it is dispersed in absolute methanol (5mL), obtains having hollow micro- anti-
Answer the Au/Cu of cavity configuration2S hetero-nanocrystals particle colloidal sols.
Step (2)：To the Au/Cu with hollow reaction microchamber structure2S hetero-nanocrystals particles, according to cation
Chemical reactivity, using cationic chemical reaction by Cu2S outer layers are converted into other sulfide semiconductors, in being had
The semiconductor-based hetero-nanocrystals of empty reaction microchamber structure；
The semiconductor-based hetero-nanocrystals particle with hollow reaction microchamber structure in the present embodiment is with hollow micro-
The Au/CdS hetero-nanocrystals particles of cavity configuration are reacted, its preparation comprises the following steps：
Step 21, the Au/Cu with hollow reaction microchamber structure for taking above-mentioned steps (1) to prepare2S hetero-nanocrystals particles
Colloidal sol (1mL), 15mL is diluted to absolute methanol, adds metal salt, be cadmium nitrate (30mg/mL, 1mL) in the present embodiment, shape
Into mixed liquor a；
Step 22, above-mentioned mixed liquor a is positioned over constant temperature in 60 DEG C of water-baths, adds TBP (50 μ L), form mixed solution b,
And continue stirring 30 minutes.In course of reaction, the color of nanocrystalline colloidal sol is gradually changed into blueness or purple by brown；
Step 23, the mixed liquor b is cooled to 25 DEG C by stirring after terminating, then under 5000 revs/min of rotating speed from
The heart 10 minutes, obtained lower sediment is dispersed in absolute methanol, obtains having the Au/CdS of hollow reaction microchamber structure different
Matter nanocrystalline colloidal sol.
The Au/CdS hetero-nanocrystals with hollow reaction microchamber structure that present embodiment is prepared pass through transmission
Electron microscope is detected, as shown in Figure 9.The Au/CdS with hollow reaction microchamber structure that present embodiment is prepared
Hetero-nanocrystals, there is potential application value in Photocatalyzed Hydrogen Production field.
Embodiment 13
With embodiment 12, difference is in step (2) that metal salt used is zinc nitrate, is finally given with hollow micro-
React the Au/ZnS hetero-nanocrystals colloidal sols of cavity configuration.What present embodiment was prepared has hollow reaction microchamber structure
Au/ZnS hetero-nanocrystals, there is potential application value in Photocatalyzed Hydrogen Production field.
Embodiment 14
With embodiment 12, difference is in step (2) that metal salt used is stannous chloride, is finally given with hollow
The Au/SnS hetero-nanocrystals colloidal sols of reaction microchamber structure.What present embodiment was prepared has hollow reaction microchamber structure
Au/SnS hetero-nanocrystals detected by transmission electron microscope, as shown in Figure 10.There to be hollow reaction microchamber knot
The Au/SnS hetero-nanocrystals colloidal sols of structure are placed in transparent quartz colorimetric utensil, are added a certain amount of aqueous solution of methylene blue, are made
The Xe lamps for being 300W with power, irradiate under visible mode, and solution absorbance declines rapidly (color shoals rapidly), illustrate this
The Au/SnS hetero-nanocrystals with hollow reaction microchamber structure that embodiment is prepared are in photocatalytic degradation methylene blue
Reaction in, there is significant catalytic effect.
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.
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