CN114436318B - Aqueous phase synthesis preparation of monodisperse Cu 2-x S nanocrystalline method - Google Patents
Aqueous phase synthesis preparation of monodisperse Cu 2-x S nanocrystalline method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 5
- 239000010949 copper Substances 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 55
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001879 copper Chemical class 0.000 claims abstract description 12
- 239000001509 sodium citrate Substances 0.000 claims abstract description 12
- 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 12
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000018417 cysteine Nutrition 0.000 claims abstract description 11
- 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
- 239000002245 particle Substances 0.000 claims description 21
- 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
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 abstract 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
- 239000002159 nanocrystal Substances 0.000 description 19
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 9
- 239000003446 ligand Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 229920001795 coordination polymer Polymers 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
- 238000001016 Ostwald ripening Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010010957 Copper deficiency Diseases 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 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
- 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
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- OESFSXYRSCBAQJ-UHFFFAOYSA-M sodium;3-carboxy-3,5-dihydroxy-5-oxopentanoate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC([O-])=O OESFSXYRSCBAQJ-UHFFFAOYSA-M 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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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 synthesis 2‑x S nanocrystalline method. The method comprises the following steps: (1) Mixing cysteine solution and copper salt solution to obtain premix; (2) Deionized water is added into a reaction container, sodium citrate solution is added, and nitrogen is introduced; (3) Adding the premix 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, adding a thioacetamide solution under the stirring condition, and stirring and reacting for 8-12 minutes; (5) Heating the system obtained in the step (4) to 65-75 ℃, and carrying out reflux reaction for 11-13 h to obtain Cu with the grain diameter of 9.5-9.7 nm 2‑x S nanocrystalline. The method successfully prepares the Cu with single dispersion and adjustable size in the aqueous solution 2‑x S nanocrystalline.
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 synthesis 2- x S nanocrystalline method.
Background
Copper vacancy imparting Cu 2-x S nanocrystals have unique properties, e.g., cu due to high carrier concentration copper deficiency 2-x S nanocrystals exhibit excellent conductivity and are a typical p-type semiconductor. In addition, copper atoms can move as rapidly as liquids at high temperatures, which 'liquid-like' behavior may significantly enhance scattering of their phonons and result in lower thermal conductivity, thus, cu 2-x S nanocrystals have wide applications in energy conversion and storage. In addition, copper vacancies cause Cu 2-x S nano-crystal Local Surface Plasmon Resonance (LSPR) has strong absorption in the near infrared region and covers near redThe optical absorption of the outer first region (NRI-I) and near infrared second region (NRI-II) biological windows can be used for multispectral Photoacoustic (PA) imaging of cancer. Cu, compared with the different kinds of contrast agents developed 2-x S 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 synthesis 2-x S nanocrystalline method, which realizes overall process control of Cu by selecting two proper ligands 2-x The nucleation growth process of the S nanocrystalline is successful to prepare the monodisperse Cu2-xS nanocrystalline with adjustable size in aqueous solution. Compared with the prior preparation method, the method is simpler and more economical.
To achieve the above object, the present invention provides a method for preparing monodisperse Cu by aqueous phase synthesis 2-x A method of S nanocrystalline comprising the steps of:
(1) Mixing cysteine solution and copper salt solution to obtain premix;
(2) Deionized water is added into a reaction container, then sodium citrate solution is added, and nitrogen is introduced;
(3) Adding the premix 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), regulating the pH value of the system obtained in the step (3) to 9.8-10.2, mixing for 8-12 minutes, adding a thioacetamide solution under stirring, and stirring for reacting for 8-12 minutes;
(5) Heating the system obtained in the step (4) to 65-75 ℃, and carrying out reflux reaction for 11-13 h to obtain Cu with the grain diameter of 9.5-9.7 nm 2-x S nanocrystalline, 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 being 40 mL.
Preferably, in the step (2), the nitrogen gas 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 to 0.52mol/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 reacting of step (3) and step (4) are carried out at room temperature.
Preferably, cu obtained in step (5) 2-x The particle size of the S nanocrystalline is 9.6nm.
The invention successfully realizes the preparation of the monodisperse and size-adjustable Cu in the water phase based on a nucleation-growth-dispersion triple modulation strategy 2-x S nanocrystalline (Cu) 2-x S NCs). The strategy is mainly to reasonably select two proper ligands so as to realize the whole process and trans-scale control of the nucleation growth process. First, in order to reduce the precursor (Cu 2+ ) By introducing a first ligand, cysteine, we will add Cu + Immobilized on n-coordination polymer (ammonium cysteine-Cu + ) Is a kind of medium. The ligand is introduced, so that on one hand, the situation that the nucleation and growth processes cannot be separated due to the fact that a system is out of control because of too fast reaction is avoided; on the other hand, cu caused by rapid precursor consumption is avoided 2-x S nanocrystals do not have enough monomer during growth to enter the ostwald ripening stage prematurely. Next, for Cu formed 2-x S nanocrystalline, due to the combination of sodium citrate (citrate) as a second ligand, cu is remarkably increased 2-x S nanocrystalline electrostatic repulsion and steric hindrance effect, thereby avoiding Cu 2-x S nanocrystals adsorb, aggregate, and fuse with each other. Cu prepared based on proposed nucleation-growth-dispersion triplet modulation (NGDTM) strategy 2-x The S nanocrystals had a particle size distribution of about 5% (i.e., a particle size of about 5% in a ratio of 9.4 to 9.8 nm), and as a result, cu was able to be synthesized with an organic phase 2-x S nano-crystalline phase rivals.
In addition, the invention is synthesized in the water phase, and the prepared material has strong absorption in the 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 is a Cu having a particle diameter of 9.6nm 2-x S, amplifying the transmission diagram step by the nanocrystalline A1;
FIG. 2 is a Cu particle size of 9.6nm 2-x S, a transmission electron microscope high-resolution image and a Fourier transform image of the nanocrystal A1;
FIG. 3 is a Cu particle size of 9.6nm 2-x XRD pattern of S nanocrystalline A1;
FIG. 4 is a Cu particle size of 9.6nm 2-x XPS diagram of S nanocrystal A1;
FIG. 5 is a Cu particle size of 9.6nm 2-x Absorption diagram of S nanocrystal A1.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for preparing monodisperse Cu by aqueous phase synthesis 2-x A method of S nanocrystalline, the method comprisingThe method comprises the following steps:
(1) Mixing cysteine solution and copper salt solution to obtain premix;
(2) Deionized water is added into a reaction container, then sodium citrate solution is added, and nitrogen is introduced;
(3) Adding the premix 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), regulating the pH value of the system obtained in the step (3) to 9.8-10.2, mixing for 8-12 minutes, adding a thioacetamide solution under stirring, and stirring for reacting for 8-12 minutes;
(5) Heating the system obtained in the step (4) to 65-75 ℃, and carrying out reflux reaction for 11-13 h to obtain Cu with the grain diameter of 9.5-9.7 nm 2-x S nanocrystalline, wherein x is more than or equal to 0 and less than or equal to 1.
The method selects two ligands to react with thioacetamide in copper salt to generate Cu 2-x Before S nanocrystalline, adding a first ligand cysteine when preparing a premix, and adding Cu in advance + Is fixed on n coordination polymer to prevent Cu from being generated by reaction 2-x The system is out of control due to too fast reaction during S nanocrystalline, which leads to incapability of separating nucleation and growth process, and can also prevent Cu caused by fast precursor consumption 2-x S nanocrystalline does not have enough monomer in the growth process, so that the S nanocrystalline enters an Ostwald ripening stage prematurely; at the same time, adding sodium citrate as a second ligand before adding thioacetamide solution to react to form Cu 2-x S nano-crystal can be combined with sodium citrate to obviously increase Cu 2-x S nanocrystalline electrostatic repulsion and steric hindrance effect, thereby avoiding Cu 2-x S nano crystals are mutually adsorbed, aggregated and fused, so that the monodisperse Cu with adjustable size is prepared in an aqueous phase 2-x S nanocrystalline (Cu) 2-x S 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 source of copper ions. In a preferred embodiment, in step (1), the copper salt solution may be a copper sulfate solution.
In a preferred embodiment, in order to bond Cu + Fully fixing the solution in an n 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 of the present invention, cu having a particle diameter of 9.5 to 9.7nm is obtained in order to obtain a monodispersed Cu 2-x S nanocrystalline, a proper amount of sodium citrate solution is needed to be added. 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 being 40 mL.
Since the precursor thioacetamide is unstable in air, nitrogen gas is required to be introduced in the step (2). In a preferred embodiment, in step (2), the nitrogen is introduced for a period of 8 to 12 minutes, for example, 8 minutes, 9 minutes, 10 minutes, 11 minutes or 12 minutes.
In step (4), in a specific embodiment, the pH of the system obtained in step (3) needs to be adjusted to 9.8 to 10.2, for example, the pH of the system obtained in 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 sodium hydroxide solution. In a more preferred embodiment, in 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 0.52mol/L.
In the process of the present invention, in order to provide the S source, it is necessary to add an appropriate amount of thioacetamide solution. In a specific embodiment, 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.
In a specific embodiment, the stirring process of step (3) and step (4) is performed at room temperature, and the mixing of step (3) and step (4) is also performed at room temperature, e.g. 25 ℃, without heating. In the step (3), the materials are mixed and simultaneously oxygen is removed.
In step (5) of the present invention, the oil bath is used for heating in order to obtain a better reaction between the raw materials, and in a specific embodiment, the system obtained in step (4) is heated to 65 to 75℃such as 65℃66℃67℃68℃69℃70℃71℃72℃73℃74℃75 ℃.
Cu is prepared by adopting the method of the invention 2-x The size of the S nanocrystalline can be controlled in a smaller range (the grain diameter is 9.5-9.7 nm). In a preferred embodiment, cu obtained in step (5) 2-x The particle size of the S nanocrystalline is 9.6nm.
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) 3mL of 0.1mol/L cysteine solution and 125 mu L of 0.4mol/L copper sulfate solution are mixed to obtain a premix;
(2) 40mL of deionized water is added into a 100mL three-neck flask, then 1mL of sodium citrate solution with the concentration of 0.1mol/L is added, and nitrogen is introduced for 10min;
(3) Adding the premix 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 stirring, and stirring and reacting for 10 minutes;
(5) Heating the system obtained in the step (4) to 70 ℃, and carrying out reflux reaction for 12 hours to obtain Cu with the grain diameter of 9.6nm 2-x S nanocrystalline A1.
Example 2
The process was carried out in accordance with example 1, except that in step (4), the thioacetamide solution was 0.009mol/L in concentration and 1.01mL in volume, to thereby obtain Cu having a particle diameter of 9.66nm 2-x S nanocrystalline A2.
Example 3
The procedure of example 1 was followed, except that in step (4), the concentration of the thioacetamide solution was 0.011mol/L and the volume was 0.99mL, to finally obtain Cu having a particle size of 9.56nm 2-x S nanocrystalline A3.
Example 4
The procedure of example 1 was followed, except that in step (1), the concentration of the cysteine solution was 0.09mol/L and the volume was 2.98mL; 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 prepared 2-x S nanocrystalline A4.
Example 5
The process of example 1 was followed, except that in step (1), the concentration of the cysteine solution was 0.11mol/L and the volume was 3.02mL; the concentration of the copper sulfate solution is 0.38mol/L, the volume is 126 mu L, and finally the Cu with the grain diameter of 9.68nm is prepared 2-x S nanocrystalline A5.
Example 6
The process was carried out in accordance with example 1, except that in step (2), the sodium citrate solution was 0.09mol/L in concentration and 1.01mL in volume, to finally obtain Cu having a particle size of 9.65nm 2-x S nanocrystalline A6.
Example 7
The procedure was carried out in accordance with example 1, except that in step (4), 0.5mol/L of 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 obtaining Cu having a particle size of 9.62nm 2-x S nanocrystalline A7.
Example 8
The procedure was carried out in accordance with example 1, except that in step (4), 0.5mol/L of 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 obtaining Cu having a particle size of 9.64nm 2-x S nano-crystal A8.
Cu prepared in examples 1-8 2-x The grain diameter of the S nanocrystalline A1-A8 is in the smaller range of 9.5-9.7 nm, and the Cu prepared by the method of the invention can be seen 2-x The S nanocrystalline size is controllable. FIG. 1 is a particle size of 9.6nmCu 2-x As can be seen from FIG. 1, the transmission diagrams of S nanocrystalline A1 with different magnification ratios, cu is prepared 2-x S nano-crystal is in a monodispersed state. FIG. 2 is a Cu particle size of 9.6nm 2-x High resolution and fourier transform of S nanocrystal A1. FIG. 3 is a Cu particle size of 9.6nm 2-x XRD pattern of S nanocrystal A1. FIG. 4 is a Cu particle size of 9.6nm 2-x XPS map of S nanocrystal A1. FIG. 5 is a Cu particle size of 9.6nm 2-x As can be seen from FIG. 5, the absorption diagram of the ultraviolet visible infrared spectrum of S nanocrystalline A1, cu 2-x S nano-crystal has absorption in near infrared, and can be used for photothermal treatment or photoacoustic imaging.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. Aqueous phase synthesis preparation of monodisperse Cu 2-x A method of S nanocrystalline, characterized in that the method comprises the steps of:
(1) Mixing cysteine solution and copper salt solution to obtain premix;
(2) Deionized water is added into a reaction container, then sodium citrate solution is added, and nitrogen is introduced;
(3) Adding the premix 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), regulating the pH value of the system obtained in the step (3) to 9.8-10.2, mixing for 8-12 minutes, adding a thioacetamide solution under stirring, and stirring for reacting for 8-12 minutes;
(5) Heating the system obtained in the step (4) to 65-75 ℃, and carrying out reflux reaction for 11-13 h to obtain Cu with the grain diameter of 9.5-9.7 nm 2-x S nanocrystalline, 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 step (1), the concentration of the cysteine solution is 0.09 to 0.11mol/L and the volume is 2.98 to 3.02mL based on the volume of the deionized water in 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 sodium hydroxide solution.
7. The method according to claim 6, wherein in the step (4), the concentration of the alkaline solution is 0.48 to 0.52mol/L.
8. The method according to claim 1, wherein in the step (4), the thioacetamide solution has a concentration of 0.009 to 0.011mol/L and a volume of 0.99 to 1.01mL 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 step (3) and step (4) are performed at room temperature.
10. According to claim 1The method is characterized in that Cu obtained in the step (5) 2-x The particle size of the S nanocrystalline is 9.6nm.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937492A (en) * | 2014-04-22 | 2014-07-23 | 桂林理工大学 | Method for preparing near infrared emission CuxS fluorescent quantum dots |
| CN105000588A (en) * | 2015-04-20 | 2015-10-28 | 河南师范大学 | Preparation method for water-soluble copper sulphide quantum dots |
| CN105236466A (en) * | 2015-09-22 | 2016-01-13 | 北京化工大学 | Nanometer material used for photothermal therapy and preparation method thereof |
| CN105902517A (en) * | 2016-05-31 | 2016-08-31 | 华南理工大学 | Preparation method and application of copper sulfide nanocapsule particle |
| CN106729733A (en) * | 2017-01-12 | 2017-05-31 | 上海工程技术大学 | A kind of cysteine/ferroso-ferric oxide/copper sulfide/bovine serum albumin(BSA) nano-complex particle and its preparation and application |
| CN107262734A (en) * | 2017-05-18 | 2017-10-20 | 安徽师范大学 | Synthesis in water Au@Cu2‑xThe method of the super nano-particles of E |
| CN109498808A (en) * | 2019-01-22 | 2019-03-22 | 福州大学 | A method of passing through electrostatic assembly controlledly synthesis CuS@EPO nano material |
| KR101977347B1 (en) * | 2018-10-01 | 2019-05-10 | 주식회사 앰트 | Copper sulfide core-shell nanoparticles including coating composition for selectively shielding near infrared ray and production of the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011066205A1 (en) * | 2009-11-25 | 2011-06-03 | E. I. Du Pont De Nemours And Company | Aqueous process for producing crystalline copper chalcogenide nanoparticles, the nanoparticles so-produced, and inks and coated substrates incorporating the nanoparticles |
| US11820672B2 (en) * | 2019-01-17 | 2023-11-21 | Nano Sono Cooperation Ltd. | Processes for preparing metal oxide semiconductor nanomaterials |
| WO2021216941A2 (en) * | 2020-04-24 | 2021-10-28 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Cu2-xs/pbs core/shell nanocrystals |
-
2022
- 2022-01-07 CN CN202210016031.0A patent/CN114436318B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937492A (en) * | 2014-04-22 | 2014-07-23 | 桂林理工大学 | Method for preparing near infrared emission CuxS fluorescent quantum dots |
| CN105000588A (en) * | 2015-04-20 | 2015-10-28 | 河南师范大学 | Preparation method for water-soluble copper sulphide quantum dots |
| CN105236466A (en) * | 2015-09-22 | 2016-01-13 | 北京化工大学 | Nanometer material used for photothermal therapy and preparation method thereof |
| CN105902517A (en) * | 2016-05-31 | 2016-08-31 | 华南理工大学 | Preparation method and application of copper sulfide nanocapsule particle |
| CN106729733A (en) * | 2017-01-12 | 2017-05-31 | 上海工程技术大学 | A kind of cysteine/ferroso-ferric oxide/copper sulfide/bovine serum albumin(BSA) nano-complex particle and its preparation and application |
| CN107262734A (en) * | 2017-05-18 | 2017-10-20 | 安徽师范大学 | Synthesis in water Au@Cu2‑xThe method of the super nano-particles of E |
| KR101977347B1 (en) * | 2018-10-01 | 2019-05-10 | 주식회사 앰트 | Copper sulfide core-shell nanoparticles including coating composition for selectively shielding near infrared ray and production of the same |
| CN109498808A (en) * | 2019-01-22 | 2019-03-22 | 福州大学 | A method of passing through electrostatic assembly controlledly synthesis CuS@EPO nano material |
Non-Patent Citations (2)
| Title |
|---|
| 水溶性CuS纳米晶的合成及其与生物大分子的作用;郭应臣;关晓艳;李凌云;陈西茹;王鹏宇;;南阳师范学院学报(第06期);第49-51页 * |
| 量子点的表面修饰、尺寸选择与荧光传感;朱昌青;夏云生;刁雪莲;张天龙;陈金龙;;安徽师范大学学报(自然科学版)(第03期);第74-80页 * |
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