CN114436318A - Aqueous phase synthesis preparation of monodisperse Cu2-xMethod for preparing S nanocrystal - Google Patents
Aqueous phase synthesis preparation of monodisperse Cu2-xMethod for preparing S nanocrystal Download PDFInfo
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- 239000002159 nanocrystal Substances 0.000 title claims abstract description 61
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000010949 copper Substances 0.000 claims abstract description 66
- 239000000243 solution Substances 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001509 sodium citrate Substances 0.000 claims abstract description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001879 copper Chemical class 0.000 claims abstract description 12
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000018417 cysteine Nutrition 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 229920001795 coordination polymer Polymers 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007626 photothermal therapy Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
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- C01G3/00—Compounds of copper
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Abstract
The invention relates to the technical field of copper sulfide nanocrystalline synthesis, and discloses a method for preparing monodisperse Cu by aqueous phase synthesis2‑xS nanocrystal method. The method comprises the following steps: (1) mixing a cysteine solution and a copper salt solution to obtain a premixed solution; (2) adding deionized water into a reaction container, adding a sodium citrate solution, and introducing nitrogen; (3) adding the premixed solution into the solution obtained in the step (2), and mixing for 4-6 minutes; (4) dropwise adding an alkaline solution into the system obtained in the step (3) to adjust the pH value to 9.8-10.2, mixing for 8-12 minutes, then adding a thioacetamide solution under the stirring condition, and stirring for reacting for 8-12 minutes; (5) heating the system obtained in the step (4) to 65-75 ℃, and performing reflux reaction for 11-13 h to obtain Cu with the particle size of 9.5-9.7 nm2‑xAnd (4) S nanocrystals. The method successfully prepares monodisperse Cu with adjustable size in aqueous solution2‑xAnd (4) S nanocrystal.
Description
Technical Field
The invention relates to the technical field of copper sulfide nanocrystalline synthesis, in particular to a method for preparing monodisperse Cu by aqueous phase synthesis2- xS nanocrystal preparation method.
Background
Copper vacancy imparting Cu2-xS nanocrystals have unique properties, e.g., Cu deficient in copper due to high carrier concentration2-xS nanocrystals exhibit excellent conductivity and are a typical p-type semiconductor. In addition, copper atoms can move as fast as liquids at high temperatures, and this "liquid-like" behavior can significantly enhance the scattering of its phonons and lead to lower thermal conductivity, and thus Cu2-xThe S nanocrystals have wide applications in energy conversion and storage. In addition, copper vacancies result in Cu2-xThe S nanocrystal Local Surface Plasmon Resonance (LSPR) has strong absorption in a near infrared region, covers the optical absorption of biological windows of a near infrared region I (NRI-I) and a near infrared region II (NRI-II), and can be used for multispectral Photoacoustic (PA) imaging of cancer. Compared to different classes of contrast agents that have been developed, Cu2-xS nanocrystals are candidates for various biological applications due to their good biocompatibility, low cost, and strong absorption.
Disclosure of Invention
The invention aims to provide a method for preparing monodisperse Cu by aqueous phase synthesis2-xThe method of S nanocrystal realizes the whole process control of Cu by selecting two suitable ligands2-xAnd in the S nanocrystal nucleation growth process, the monodisperse Cu2-xS nanocrystal with adjustable size is successfully prepared in the aqueous solution. Compared with the prior preparation method, the method is simpler and more economical.
In order to achieve the aim, the invention provides a method for preparing monodisperse Cu by aqueous phase synthesis2-xA method of S nanocrystals, the method comprising the steps of:
(1) mixing the cysteine solution and the copper salt solution to obtain a premixed solution;
(2) adding deionized water into a reaction container, then adding a sodium citrate solution, and introducing nitrogen;
(3) adding the premixed solution obtained in the step (1) into the solution obtained in the step (2) under the stirring condition, and mixing for 4-6 minutes;
(4) dropwise adding an alkaline solution into the system obtained in the step (3), adjusting the pH value of the system obtained in the step (3) to 9.8-10.2, mixing for 8-12 minutes, then adding a thioacetamide solution under the condition of stirring, and stirring for reacting for 8-12 minutes;
(5) heating the system obtained in the step (4) to 65-75 ℃, and performing reflux reaction for 11-13 h to obtain Cu with the particle size of 9.5-9.7 nm2-xAnd (3) S nanocrystal, wherein x is more than or equal to 0 and less than or equal to 1.
Preferably, in step (1), the copper salt solution may be a copper sulfate solution or a copper chloride solution.
More preferably, in the step (1), the concentration of the cysteine solution is 0.09-0.11 mol/L and the volume is 2.98-3.02 mL based on the volume of the deionized water in the step (2) being 40 mL; the concentration of the copper salt solution is 0.38-0.42 mol/L, and the volume is 124-126 mu L.
Preferably, in the step (2), the concentration of the sodium citrate solution is 0.09-0.11 mol/L and the volume is 0.99-1.01 mL based on the volume of the deionized water of 40 mL.
Preferably, in the step (2), the nitrogen is introduced for 8 to 12 minutes.
Preferably, in step (4), the alkaline solution is a sodium hydroxide solution.
More preferably, in the step (4), the concentration of the alkaline solution is 0.48-0.52 mol/L.
Preferably, in the step (4), the concentration of the thioacetamide solution is 0.009-0.011 mol/L and the volume is 0.99-1.01 mL based on the volume of the deionized water in the step (2) being 40 mL.
Preferably, the stirring and reaction of step (3) and step (4) are carried out at room temperature.
Preferably, Cu obtained in step (5)2-xThe grain diameter of the S nanocrystal is 9.6 nm.
The invention successfully realizes the preparation of monodisperse Cu with adjustable size in the water phase based on the 'nucleation-growth-dispersion triple modulation' strategy2-xS nanocrystal (Cu)2-xS NCs). The strategy is mainly to realize the whole process and cross-scale control of the nucleation growth process by reasonably selecting two suitable ligands. First, to reduce the precursor (Cu)2+) By introducing a first ligand, cysteine, Cu+Immobilization on n-coordination polymers (ammonium-Cytosilate-Cu)+) In (1). On one hand, the introduction of the ligand avoids the condition that the nucleation and the growth processes can not be separated due to the fact that the system is out of control due to the fact that the reaction is too fast; on the other hand, avoiding Cu caused by rapid consumption of precursor2-xThe S nanocrystals do not have enough monomer in the growth process to enter the ostwald ripening stage prematurely.Second, for the Cu formed2-xS nanocrystal, due to the combination of a second ligand sodium citrate (citrate), significantly increases Cu2-xElectrostatic repulsion and steric hindrance effect of S-nanocrystal to avoid Cu2-xAdsorption, aggregation and fusion of S nanocrystals to each other. Cu prepared based on proposed nucleation-growth-dispersion triple modulation (NGDTM) strategy2-xThe S nanocrystal has a particle size distribution of about 5% (i.e., a ratio of about 5% for a particle size of 9.4 to 9.8 nm), and as a result, can be synthesized with Cu in an organic phase2-xThe S nanocrystal phase is comparable.
In addition, the invention is synthesized in aqueous phase, and the prepared material has strong absorption in near infrared, so that the prepared material has better biocompatibility and has good biological application prospect in the aspects of photoacoustic imaging, cancer treatment and the like.
Drawings
FIG. 1 shows Cu having a particle size of 9.6nm2-xA step-by-step enlarged transmission diagram of the S nanocrystal A1;
FIG. 2 is Cu with a particle size of 9.6nm2-xA transmission electron microscope high resolution image and a Fourier transform image of the S nanocrystal A1;
FIG. 3 is Cu with a particle size of 9.6nm2-xXRD pattern of S nanocrystal a 1;
FIG. 4 is Cu with a particle size of 9.6nm2-xXPS plot of S nanocrystal a 1;
FIG. 5 shows Cu having a particle size of 9.6nm2-xAbsorption diagram of S nanocrystal a 1.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing monodisperse Cu by aqueous phase synthesis2-xA method of S nanocrystals, the method comprising the steps of:
(1) mixing the cysteine solution and the copper salt solution to obtain a premixed solution;
(2) adding deionized water into a reaction container, then adding a sodium citrate solution, and introducing nitrogen;
(3) adding the premixed solution obtained in the step (1) into the solution obtained in the step (2) under the stirring condition, and mixing for 4-6 minutes;
(4) dropwise adding an alkaline solution into the system obtained in the step (3) to adjust the pH value of the system obtained in the step (3) to 9.8-10.2, mixing for 8-12 minutes, then adding a thioacetamide solution under a stirring condition, and stirring for reacting for 8-12 minutes;
(5) heating the system obtained in the step (4) to 65-75 ℃, and performing reflux reaction for 11-13 h to obtain Cu with the particle size of 9.5-9.7 nm2-xAnd (3) S nanocrystal, wherein x is more than or equal to 0 and less than or equal to 1.
The method selects two ligands, and Cu is generated by the reaction of copper salt and thioacetamide2-xBefore S nanocrystal, a first ligand cysteine is added when a premixed solution is prepared, and Cu is added in advance+Immobilization on n-coordination polymers to prevent reaction to form Cu2-xThe system is out of control due to the over-fast reaction in the S nanocrystalline, so that the nucleation and growth processes can not be separated, and the Cu caused by the rapid consumption of the precursor can be prevented2-xThe S nanocrystal does not have enough monomers in the growth process, so that the S nanocrystal enters an Ostwald curing stage too early; at the same time, a second ligand sodium citrate is added before the thioacetamide solution is added, and Cu formed by reaction2-xThe S nanocrystal can be combined with sodium citrate to obviously increase Cu2-xElectrostatic repulsion and steric hindrance effect of S-nanocrystal to avoid Cu2-xThe S nanocrystals are adsorbed, aggregated and fused with each other, so that the monodisperse Cu with adjustable size is prepared in the water phase2-xS nanocrystal (Cu)2-xS NCs)。
In a specific embodiment, in step (1), the copper salt solution may be a copper sulfate solution or a copper chloride solution in order to better provide a copper ion source. In a preferred embodiment, in step (1), the copper salt solution may be a copper sulfate solution.
In a preferred embodiment, to incorporate Cu+Fully fixing the N-type coordination polymer in the n-type coordination polymer, wherein in the step (1), the concentration of the cysteine solution is 0.09-0.11 mol/L and the volume is 2.98-3.02 mL based on the volume of the deionized water in the step (2) being 40 mL; the concentration of the copper salt solution is 0.38-0.42 mol/L, and the volume is 124-126 mu L.
In the method, Cu with the particle size of 9.5-9.7 nm is monodisperse2-xAnd (4) adding a proper amount of proper sodium citrate solution into the S nanocrystal. In a preferred embodiment, in the step (2), the concentration of the sodium citrate solution is 0.09-0.11 mol/L and the volume is 0.99-1.01 mL based on the volume of the deionized water of 40 mL.
Since the thioacetamide precursor is unstable in air, nitrogen gas is required to be introduced in the step (2). In a preferred embodiment, in the step (2), the nitrogen gas is introduced for 8 to 12 minutes, for example, 8 minutes, 9 minutes, 10 minutes, 11 minutes, or 12 minutes.
In the step (4), in a specific embodiment, the pH of the system obtained in the step (3) needs to be adjusted to 9.8 to 10.2, and for example, the pH of the system obtained in the step (3) may be adjusted to 9.8, 9.9, 10, 10.1 or 10.2.
In a preferred embodiment, in step (4), the alkaline solution is a sodium hydroxide solution. In a more preferred embodiment, in the step (4), the concentration of the alkaline solution is 0.48 to 0.52mol/L, and may be, for example, 0.48mol/L, 0.49mol/L, 0.5mol/L, 0.51mol/L, or 0.52 mol/L.
In the process of the present invention, a suitable amount of thioacetamide solution is added in order to provide the source of S. In a specific embodiment, in the step (4), based on the volume of the deionized water in the step (2) being 40mL, the concentration of the thioacetamide solution is 0.009-0.011 mol/L, and the volume is 0.99-1.01 mL.
In a specific embodiment, the stirring process in step (3) and step (4) is performed at room temperature, and the mixing in step (3) and step (4) is also performed at room temperature, for example, at 25 ℃, without heating. In the step (3), the oxygen is removed while the materials are mixed.
In step (5) of the present invention, the reaction between the raw materials is preferably carried out by heating in an oil bath, and in a specific embodiment, the temperature of the system obtained in step (4) is raised to 65 to 75 ℃, and may be, for example, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃ or 75 ℃.
The method of the invention is adopted to prepare Cu2-xThe size of the S nanocrystal can be controlled in a smaller range (the particle size is 9.5-9.7 nm). In a preferred embodiment, the Cu obtained in step (5)2-xThe grain diameter of the S nanocrystal is 9.6 nm.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
Example 1
(1) Mixing 3mL of cysteine solution with 0.1mol/L and 125 mu L of copper sulfate solution with 0.4mol/L to obtain a premixed solution;
(2) adding 40mL of deionized water into a 100mL three-neck flask, then adding 1mL of 0.1mol/L sodium citrate solution, and introducing nitrogen for 10 min;
(3) adding the premixed solution obtained in the step (1) into the solution obtained in the step (2) under the condition of stirring at room temperature, and reacting for 5 minutes;
(4) dropwise adding 0.5mol/L sodium hydroxide solution into the system obtained in the step (3) to adjust the pH value of the system obtained in the step (3) to 10, reacting for 10 minutes, then adding 1mL of 0.01mol/L thioacetamide solution under the stirring condition, and stirring and reacting for 10 minutes;
(5) heating the system obtained in the step (4) to 70 ℃, and carrying out reflux reaction for 12h to obtain Cu with the particle size of 9.6nm2-xS nanocrystal a 1.
Example 2
Is carried out as in example 1, except thatIn the step (4), the concentration of the thioacetamide solution is 0.009mol/L, the volume is 1.01mL, and finally Cu with the particle size of 9.66nm is prepared2-xS nanocrystal a 2.
Example 3
The procedure of example 1 was followed, except that, in the step (4), the thioacetamide solution was used in a concentration of 0.011mol/L and a volume of 0.99mL, to finally obtain Cu having a particle diameter of 9.56nm2-xS nanocrystal a 3.
Example 4
The procedure was followed as in example 1, except that, in step (1), the cysteine solution was 0.09mol/L in volume of 2.98 mL; the concentration of the copper sulfate solution is 0.42mol/L, the volume is 124 mu L, and finally the Cu with the grain diameter of 9.52nm is prepared2-xS nanocrystal a 4.
Example 5
The procedure was followed as in example 1, except that, in step (1), the cysteine solution was 0.11mol/L in volume of 3.02 mL; the concentration of the copper sulfate solution is 0.38mol/L, the volume is 126 mu L, and finally Cu with the grain diameter of 9.68nm is prepared2-xS nanocrystal a 5.
Example 6
The procedure of example 1 was followed, except that, in the step (2), the sodium citrate solution was used in a concentration of 0.09mol/L and a volume of 1.01mL, to finally obtain Cu having a particle size of 9.65nm2-xS nanocrystal a 6.
Example 7
The procedure of example 1 was followed, except that in step (4), 0.5mol/L sodium hydroxide solution was added dropwise to the system obtained in step (3) to adjust the pH of the system obtained in step (3) to 10.2, thereby finally obtaining Cu having a particle size of 9.62nm2-xS nanocrystal a 7.
Example 8
The procedure of example 1 was followed, except that in step (4), 0.5mol/L sodium hydroxide solution was added dropwise to the system obtained in step (3) to adjust the pH of the system obtained in step (3) to 9.8, thereby finally obtaining Cu having a particle size of 9.64nm2-xS nanocrystal A8.
Cu prepared in examples 1 to 82-xThe grain size of the S nanocrystal A1-A8 is in a smaller range of 9.5-9.7 nm, so that the Cu prepared by the method disclosed by the invention2-xThe size of the S nanocrystal is controllable. FIG. 1 shows Cu having a particle size of 9.6nm2-xTransmission diagram of S nano crystal A1 with different magnification, as can be seen from FIG. 1, the prepared Cu2-xThe S nanocrystals are in a monodisperse state. FIG. 2 is Cu with a particle size of 9.6nm2-xHigh resolution and fourier transform plots of S nanocrystal a 1. FIG. 3 is Cu with a particle size of 9.6nm2-xXRD pattern of S nanocrystal a 1. FIG. 4 is Cu with a particle size of 9.6nm2-xXPS plot of S nanocrystal a 1. FIG. 5 shows Cu having a particle size of 9.6nm2-xThe absorption diagram of the ultraviolet-visible infrared spectrum of the S nanocrystal A1 is shown in FIG. 5, and Cu is shown2-xThe S nanocrystal has absorption in near infrared, and can be used for photothermal therapy or photoacoustic imaging.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. Aqueous phase synthesis preparation of monodisperse Cu2-xThe method of S nanocrystals is characterized by comprising the following steps:
(1) mixing the cysteine solution and the copper salt solution to obtain a premixed solution;
(2) adding deionized water into a reaction container, then adding a sodium citrate solution, and introducing nitrogen;
(3) adding the premixed solution obtained in the step (1) into the solution obtained in the step (2) under the stirring condition, and mixing for 4-6 minutes;
(4) dropwise adding an alkaline solution into the system obtained in the step (3), adjusting the pH value of the system obtained in the step (3) to 9.8-10.2, mixing for 8-12 minutes, then adding a thioacetamide solution under the condition of stirring, and stirring for reacting for 8-12 minutes;
(5) will be described in detail(4) Heating the obtained system to 65-75 ℃, and carrying out reflux reaction for 11-13 h to obtain Cu with the particle size of 9.5-9.7 nm2-xAnd (3) S nanocrystal, wherein x is more than or equal to 0 and less than or equal to 1.
2. The method according to claim 1, wherein in step (1), the copper salt solution may be a copper sulfate solution or a copper chloride solution.
3. The method according to claim 1 or 2, wherein in the step (1), the concentration of the cysteine solution is 0.09-0.11 mol/L and the volume is 2.98-3.02 mL based on the volume of the deionized water in the step (2) being 40 mL; the concentration of the copper salt solution is 0.38-0.42 mol/L, and the volume is 124-126 mu L.
4. The method according to claim 1, wherein in the step (2), the concentration of the sodium citrate solution is 0.09-0.11 mol/L and the volume is 0.99-1.01 mL based on the volume of the deionized water being 40 mL.
5. The method according to claim 1, wherein in the step (2), the nitrogen gas is introduced for 8 to 12 minutes.
6. The method according to claim 1, wherein in step (4), the alkaline solution is a sodium hydroxide solution.
7. The method according to claim 6, wherein in the step (4), the concentration of the alkaline solution is 0.48-0.52 mol/L.
8. The method according to claim 1, wherein in the step (4), the thioacetamide solution has a concentration of 0.009-0.011 mol/L and a volume of 0.99-1.01 mL based on the volume of the deionized water of 40mL in the step (2).
9. The method of claim 1, wherein the agitating and mixing of steps (3) and (4) is performed at room temperature.
10. The method of claim 1, wherein the Cu obtained in step (5)2-xThe grain diameter of the S nanocrystal is 9.6 nm.
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