CN115007177A - CdSeS magic number nanocluster and application thereof as photocatalyst - Google Patents

CdSeS magic number nanocluster and application thereof as photocatalyst Download PDF

Info

Publication number
CN115007177A
CN115007177A CN202210688800.1A CN202210688800A CN115007177A CN 115007177 A CN115007177 A CN 115007177A CN 202210688800 A CN202210688800 A CN 202210688800A CN 115007177 A CN115007177 A CN 115007177A
Authority
CN
China
Prior art keywords
cdses
nanocluster
raw material
magic
selenium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210688800.1A
Other languages
Chinese (zh)
Other versions
CN115007177B (en
Inventor
刘跃辉
余睽
沈悦海
孙郭程港
张猛
陈晓琴
栾超然
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Original Assignee
Sichuan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan University filed Critical Sichuan University
Priority to CN202210688800.1A priority Critical patent/CN115007177B/en
Publication of CN115007177A publication Critical patent/CN115007177A/en
Application granted granted Critical
Publication of CN115007177B publication Critical patent/CN115007177B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0573—Selenium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C01G11/006—Compounds containing, besides cadmium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/18—Oxygen atoms
    • C07D263/20—Oxygen atoms attached in position 2
    • C07D263/26—Oxygen atoms attached in position 2 with hetero atoms or acyl radicals directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of semiconductor magic-number nanocluster catalytic materials, and particularly relates to a CdSeS magic-number nanocluster and application thereof as a photocatalyst. The CdSeS magic number nanocluster is prepared by the following method: the cadmium-selenium-containing sulfur-bearing material is prepared from a cadmium source, a selenium-containing raw material and a sulfur-containing raw material, wherein the molar ratio of Cd, Se to S in the raw material is 20: (5-10): (1-5); the cadmium source is one or a mixture of cadmium tetradecanoate and cadmium oleate; the selenium-containing raw material is selected from one or a mixture of two or more of selenium powder, a CdSe induction period sample and a CdSe magic number nanocluster; the sulfur-containing raw material is selected from one or a mixture of two of sulfur powder and a CdS induction period sample. The invention provides a low-cost choice for the synthesis of amino acid derivatives and has good application prospect.

Description

CdSeS magic number nanocluster and application thereof as photocatalyst
Technical Field
The invention belongs to the technical field of semiconductor magic-number nanocluster catalytic materials, and particularly relates to a CdSeS magic-number nanocluster and application thereof as a photocatalyst.
Background
Magic nanoclusters are a class of materials that intervene between molecules and conventional crystals, and their specific structure is unknown. The magic number nanoclusters of CdS, CdSe and the like are semiconductor luminescent materials. In addition, there have been many studies on the complex magic number nanoclusters of CdS and CdSe, for example: the Chinese patent application CN113046083A discloses a luminescent magic-number nanocluster, a preparation method and application thereof, and provides a CdSeS magic-number nanocluster emitting blue light. The semiconductor luminescent material is a material which releases energy to emit light through the recombination of electrons and holes, and has great application prospects in the fields of luminescent devices, photocatalysis and the like.
In the preparation process of amino acid, reduction of imido ester is one of the most common and widely applied methods, amino acid ester can be efficiently prepared by the method, and then the amino acid can be obtained through simple deprotection. The reduction method of the imidate mainly includes two methods of direct hydrogenation and transfer hydrogenation. The method for reducing the imidate by transfer hydrogenation mainly carries out hydrogenation in a manner that the traditional hydrogen source is catalyzed by noble metal, and has the defects of higher cost and harsh reaction conditions.
The Chinese patent application CN114436871A discloses a preparation method of amino acid ester or deuterated amino acid ester compounds, which comprises the following steps: the imidate can perform a photocatalytic reaction under blue light irradiation, thereby preparing the amino acid ester. However, the method needs to use a photosensitizer, and the existing photosensitizer material is generally a noble metal salt compound, so that the problem of high cost still exists.
Therefore, it would be a great challenge and opportunity to develop a new, green, simple to synthesize, inexpensive photocatalyst to replace noble metal catalysis. The semiconductor magic-number nanocluster catalytic material can promote separation and recombination of electrons and holes through illumination, so that the semiconductor magic-number nanocluster catalytic material has great application potential in the field of photocatalysis. However, the catalytic mechanism of such catalysts is not fully understood. Research shows that even the semiconductor magic-number nanocluster materials with similar structure compositions and close light-emitting wavelengths have great difference on the catalytic performance of the reaction.
Therefore, there is no report that the semiconductor phantom nanoclusters are used as a photocatalyst for reduction of imidate.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a CdSeS magic-number nanocluster and application thereof as a photocatalyst. Aims to provide a semiconductor magic number nanocluster catalytic material to realize the aim of preparing amino acid derivatives by photocatalytic reduction of imidate. The amino acid derivative can be further used as an intermediate for preparing amino acid compounds, and provides a low-cost method for introducing amino acid fragments into drug design synthesis, practical chemicals and natural products.
A CdSeS magic number nanocluster is prepared by the following method: mixing a cadmium source, a selenium-containing raw material and a sulfur-containing raw material for reaction to obtain the cadmium-containing material;
the cadmium source is one or a mixture of two of cadmium tetradecanoate and cadmium oleate, the selenium-containing raw material is one or a mixture of two or more of selenium powder, a CdSe induction period sample and a CdSe magic number nanocluster, and the sulfur-containing raw material is one or a mixture of two of sulfur powder and a CdS induction period sample;
the feeding ratio of the cadmium source to the selenium-containing raw material to the sulfur-containing raw material meets the condition that the molar ratio of Cd to Se to S is 20: (5-10): (1-5), preferably 20: 5: 2.5.
preferably, the selenium-containing raw material is selenium powder, and the sulfur-containing raw material is sulfur powder.
Preferably, the reaction conditions for preparing the CdSeS magic number nanoclusters are as follows: the temperature is 230 ℃ and 250 ℃, the time is 30-180 minutes, and the solvent is 1-octadecene.
Preferably, the reaction conditions for preparing the CdSeS magic number nanoclusters are as follows: the temperature was 230 ℃ for 60 minutes.
Preferably, the feeding ratio of the cadmium source, the selenium-containing raw material and the sulfur-containing raw material meets the condition that the molar ratio of Cd, Se and S is 20: 5: 2.5.
the invention also provides application of the CdSeS magic-number nanocluster as a photocatalyst.
The invention also provides a preparation method of the amino acid derivative, which is characterized in that imine compound A and alkyl active ester B are subjected to photochemical reaction under the action of blue light and a photocatalyst to generate the amino acid derivative, and the reaction formula is as follows:
Figure BDA0003700768610000021
wherein R is 1 、R 2 Are each independently selected from C 1 -C 10 Alkyl groups of (a);
the photocatalyst is the CdSeS magic number nanocluster.
Preferably, the reaction formula is:
Figure BDA0003700768610000031
preferably, in the photochemical reaction, the photocatalyst, the imine compound a and the alkyl active ester B are used in a ratio of (5-200 mg): 0.5 mmol: (0.5-3mmol), or the photochemical reaction is carried out for 4-8 h.
Preferably, in the photochemical reaction, the ratio of the photocatalyst, the imine compound a and the alkyl active ester B is 100 mg: 0.5 mmol: 0.75mmol, or the photochemical reaction time was 4 h.
Preferably, the photochemical reaction is carried out under the action of a base, wherein the base is one or a mixture of two or more of potassium carbonate, potassium phosphate, monopotassium phosphate, cesium carbonate or pyridine, and is preferably potassium carbonate;
and/or the photochemical reaction is carried out under the action of a reducing agent, wherein the reducing agent is selected from one or a mixture of two or more of 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester, N-diisopropylethylamine, triethylamine or 1, 8-diazabicycloundece-7-ene, and is preferably 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester;
and/or the photochemical reaction is carried out in a solvent, wherein the solvent is one or a mixture of two or more of dichloromethane, 1, 2-dichloroethylene, dimethyl sulfoxide, N-dimethylformamide or acetonitrile, and dichloromethane is preferred.
The Induction Period Sample (IPS) is an intermediate provided by the teaching subjects of Helianthus tuberosus (chem. Mater.2017,29, 5727-5735; nat. Commun.2017,8,15467; J. Phys. chem. Lett.2018,9, 2818-2824; adv. Sci.2018,5,1800632), wherein the effective component is a precursor compound, and the precursor compound does not show characteristic ultraviolet absorption at the end of synthesis, but can be converted into corresponding magic number nanoclusters (MSC) through a period of incubation time or by adding additives, and then shows ultraviolet characteristic absorption. Wherein, the induction phase sample used in the invention can be synthesized by referring to the prior art (J.Phys.chem.Lett.2018,9,6356-6363 or the Chinese patent application CN 113046083A).
The CdSeS magic-number nanocluster is obtained by adding a CdS monomer to a CdSe magic-number nanocluster. The semiconductor solar cell has a semiconductor energy band structure, photoinduced charge-hole separation recombination capability and improved photocatalytic performance. Meanwhile, the magic-number nanocluster is formed by adding CdS monomers into the CdSe magic-number nanocluster, the particle size of the nanocluster cannot be increased in the process, so that an emission peak cannot be red-shifted, and the purity of a blue light material is guaranteed. The luminescent properties of the magic number nanoclusters CdSeS dMSC-455 specifically synthesized in the examples are as follows: the absorption peak is located at 450-460nm, the emission wavelength is located at 455-465nm, and the half-peak width is less than 12 nm.
The invention discovers for the first time that the CdSeS magic-number nanoclusters can be used as a photocatalyst to catalyze the reduction of imidic acid ester to obtain an amino acid derivative. In addition, the CdSeS magic-number nanoclusters provided by the invention have higher yield compared with CdSeS quantum dots, CdSe magic-number nanoclusters and CdS magic-number nanoclusters with core-shell structures. The invention provides a low-cost choice for the synthesis of amino acid derivatives, and the amino acid derivatives obtained by the invention can be further used as intermediates for preparing amino acid compounds, and provides a low-cost method for introducing amino acid fragments into drug design synthesis, practical chemicals and natural products. Therefore, the invention has good application prospect.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is an XRD characterization of CdSeS dMSC-455 prepared in example 1;
FIG. 2 shows the absorption and emission spectra of CdSeS dMSC-455 prepared in example 1;
FIG. 3 shows the hydrogen spectrum and carbon spectrum nuclear magnetic data of amino acid derivatives obtained by the reduction and addition of CdSeS dMSC-455 serving as a photocatalyst in example 1;
FIG. 4 is the high resolution mass spectrum data of amino acid derivatives obtained by the reduction and addition of CdSeS dMSC-455 in example 1 as a photocatalyst.
Detailed Description
Among the reagents and materials used in the following examples and experimental examples, those not specifically mentioned are commercially available.
EXAMPLE 1 preparation of amino acid derivatives
1. Preparation of CdSeS dMSC-455
(1) Preparation of cadmium tetradecanoate (Cd (MA)) 2 ) A precursor; the method comprises the following specific steps:
placing cadmium oxide (1.284g, 10mmol), tetradecanoic acid (5.253g, 23mmol) and 1-octadecene (43.692g) in a 250mL three-neck flask;
vacuum was applied at room temperature, vacuum/nitrogen was applied three times (completed within 30 minutes), and stirred at 80 ℃ for 60 minutes;
heating to 240 ℃ under the protection of nitrogen, and reacting for 3 hours;
cooling to 110 ℃, and exhausting for 60 minutes to obtain the product, namely the cadmium tetradecanoate precursor.
(2) Placing a cadmium tetradecanoate precursor (3g, 0.6mmol), selenium powder (0.0118g, 0.15mmol), sulfur powder (0.0024g, 0.075mmol) and 1-octadecene (4.5g) in a 50mL three-neck flask;
(3) vacuumizing for 30 minutes at room temperature, and performing vacuum/nitrogen gas replacement three times (completed within 30 minutes); and evacuated at 110 ℃ for 30 minutes.
(4) Adding glacial acetic acid under the protection of nitrogen, stirring and reacting for 30 minutes at 110 ℃;
(5) under the protection of nitrogen, the temperature is raised to 230 ℃, and the reaction is carried out for 60 minutes, thus synthesizing the target product CdSeS dMSC-455 MSC.
2. Characterization of CdSeS dMSC-455
XRD characterization of CdSeS dMSC-455 prepared by the above method is shown in FIG. 1.
The second curve (middle) in the XRD data pattern is the XRD measurement results for the sample. The results were matched to some extent, but were different, with the CdS sphalerite crystal form standard card (at the top) and the CdSe sphalerite crystal form standard card (at the bottom). The characterization result by XRD can be presumed that the sample structure is based on sphalerite CdSe, and part of Se atoms are replaced by S atoms. Meanwhile, the proportion of the doped S element is extremely low, because no diffraction peak which is matched with the CdS sphalerite standard card is shown on XRD.
The absorption spectrum (UV) and emission spectrum (PL) of the CdSeS dMSC-455 of this example are shown in FIG. 2. From the emission spectrum, it can be seen that the emission peak is located at 462nm, and is blue-shifted with respect to the emission peak of other existing CdSe @ CdS composite materials (j.am. chem. soc.2012,134, 19685-19693). In addition, the emission peak half-width was about 12nm, and no defect state emission was observed, and the relative quantum yield was 85%. Therefore, the CdSeS dMSC-455 provided by the invention can emit blue light with narrow emission bandwidth and no defects.
3. Catalytic property of CdSeS dMSC-455 magic number nanocluster as photocatalytic material participating in synthesis of amino acid derivative
The CdSeS dMSC-455 magic number nanoclusters are used as a photocatalyst for synthesizing amino acid derivatives, and the method specifically comprises the following steps of:
(1) putting imine SM1(90mg, 0.5mmol), alkyl active ester SM2(174mg, 0.75mmol), catalyst CdSeS dMSC-455(60mg), potassium carbonate (138mg, 1mmol), diethyl 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylate (HE, 190mg, 0.75mmol) and dichloromethane (9mL) into a 50mL three-neck flask, and irradiating under a 45W blue light lamp under the protection of nitrogen;
HE structural formula is as follows:
Figure BDA0003700768610000061
(2) reacting for 4 hours at room temperature under the protection of nitrogen;
(3) after the reaction is finished, directly concentrating the mixture to be dry by a rotary evaporator;
(4) column chromatography with petroleum ether/ethyl acetate as eluent gave 49mg (TM-1a) of product in 43% yield.
The reaction equation is as follows:
Figure BDA0003700768610000062
the hydrogen and carbon spectra data of TM-1a are shown in FIG. 3, and the mass spectra data are shown in FIG. 4, wherein the mass spectrum peak positions are consistent with the literature (J.org.chem.2019,84,8177-8184.), which proves that TM-1a is indeed successfully synthesized in this example.
Comparative example 1 conventional core-shell alloy quantum dots
(1) Preparation of cadmium tetradecanoate (Cd (MA)) 2 ) A precursor; the method comprises the following specific steps:
placing cadmium oxide (1.284g, 10mmol), tetradecanoic acid (5.253g, 23mmol) and 1-octadecene (43.692g) in a 250mL three-neck flask;
vacuum was applied at room temperature, vacuum/nitrogen was applied three times (completed within 30 minutes), and stirred at 80 ℃ for 60 minutes;
heating to 240 ℃ under the protection of nitrogen, and reacting for 3 hours;
cooling to 110 ℃, and exhausting for 60 minutes to obtain the product, namely the cadmium tetradecanoate precursor.
(2) Placing a cadmium tetradecanoate precursor (3g, 0.6mmol), selenium powder (0.0118g, 0.15mmol), sulfur powder (0.0024g, 0.075mmol) and 1-octadecene (4.5g) in a 50mL three-neck flask;
(3) vacuumizing for 30 minutes at room temperature, and performing vacuum/nitrogen gas replacement three times (completed within 30 minutes); and evacuated at 110 ℃ for 30 minutes.
(4) Stirring and reacting for 30 minutes at the constant temperature of 110 ℃ under the protection of nitrogen;
(5) heating to 230 ℃ under the protection of nitrogen, reacting for 60 minutes, and synthesizing the conventional core-shell alloy quantum dot
The absorption wavelength of the conventional core-shell alloy quantum dot is at 533nm and 465nm, and the emission wavelength is at 624 nm.
Comparative example 2 CdSe phantom nanoclusters
(1) Preparation of cadmium tetradecanoate (Cd (MA)) 2 ) A precursor; the method comprises the following specific steps:
placing cadmium oxide (1.284g, 10mmol), tetradecanoic acid (5.253g, 23mmol) and 1-octadecene (43.692g) in a 250mL three-neck flask;
vacuum was applied at room temperature, vacuum/nitrogen was applied three times (completed within 30 minutes), and stirred at 80 ℃ for 60 minutes;
heating to 240 ℃ under the protection of nitrogen, and reacting for 3 hours;
cooling to 110 ℃, and exhausting for 60 minutes to obtain the product, namely the cadmium tetradecanoate precursor.
(2) Placing a cadmium tetradecanoate precursor (3g, 0.6mmol), selenium powder (0.0118g, 0.15mmol) and 1-octadecene (4.5g) in a 50mL three-neck flask;
(3) vacuumizing for 30 minutes at room temperature, and performing vacuum/nitrogen gas replacement three times (completed within 30 minutes); and evacuated at 110 ℃ for 30 minutes.
(4) Under the protection of nitrogen, adding glacial acetic acid, stirring and reacting for 30 minutes at 110 ℃;
(5) under the protection of nitrogen, the temperature is raised to 230 ℃, and the reaction is carried out for 30 minutes, thus synthesizing the CdSe magic-number nanocluster.
The absorption wavelength of the CdSe magic-number nanoclusters is 462nm and 434nm, and the emission wavelength is 466 nm.
Comparative example 3 CdS magic number nanocluster
(1) Preparation of cadmium tetradecanoate (Cd (MA)) 2 ) A precursor; the method comprises the following specific steps:
placing cadmium oxide (1.284g, 10mmol), tetradecanoic acid (5.253g, 23mmol) and 1-octadecene (43.692g) in a 250mL three-neck flask;
vacuum was applied at room temperature, vacuum/nitrogen was applied three times (completed within 30 minutes), and stirred at 80 ℃ for 60 minutes;
heating to 240 ℃ under the protection of nitrogen, and reacting for 3 hours;
cooling to 110 ℃, and exhausting for 60 minutes to obtain the product, namely the cadmium tetradecanoate precursor.
(2) Placing a cadmium tetradecanoate precursor (3g, 0.6mmol), sulfur powder (0.0024g, 0.075mmol) and 1-octadecene (4.5g) in a 50mL three-neck flask;
(3) vacuumizing for 30 minutes at room temperature, and performing vacuum/nitrogen gas replacement three times (completed within 30 minutes); and evacuated at 110 ℃ for 30 minutes.
(4) Adding glacial acetic acid under the protection of nitrogen, stirring and reacting for 30 minutes at 110 ℃;
(5) and under the protection of nitrogen, heating to 230 ℃, and reacting for 15 minutes to synthesize the CdS magic-number nanocluster.
The absorption wavelength of the CdS magic number nanocluster is 374nm, and the emission wavelength of the CdS magic number nanocluster is 387 nm.
The advantageous effects of the present invention will be further described below by experiments.
Experimental example 1 comparison of catalytic Properties of photocatalyst
The kind of photocatalyst is preferable in this experimental example.
The experimental group was set as follows:
(1) the catalyst in the number 1 is the magic-number nanocluster cdsesdsmsc-455 prepared in example 1;
(2) the catalyst in number 2 is the core-shell alloy quantum dot prepared in comparative example 1;
(3) the catalyst in the number 3 is the CdSe magic-number nanocluster prepared in the comparative example 2;
(4) the catalyst in number 4 is the CdS phantom nanocluster prepared in comparative example 3;
(5) no. 5 catalyst was involved in the imine reduction reaction.
The amount of the photocatalyst used was 20mg, and the synthesis conditions other than those not described were the same as in section 3 of example 1.
The product yields for each experimental group are shown in the table below:
numbering Photocatalyst and process for producing the same Wavelength of light emission Yield of
1 CdSeSdMSC-455 462nm 52％
2 CdSeS core-shell alloy quantum dot 624nm 28％
3 CdSe magic-number nanoclusters 466nm 44％
4 CdS phantom nanocluster 387nm 12％
5 Is free of - 5％
The experiment shows that in a series of photocatalysts with similar structures and light emission performances, the CdSeS magic-number nanocluster provided by the invention can obviously improve the yield of a synthesis reaction and has the best catalytic performance.
Experimental example 2 optimization of reaction conditions
In this experimental example, reaction conditions for synthesizing an amino acid derivative are preferable, and reaction steps and conditions not particularly described are the same as those in example 1.
The results of comparative experiments on reaction conditions are shown in the following table:
Figure BDA0003700768610000091
the experimental results show that the yield of the reaction is improved along with the increase of the dosage of the CdSeS dMSC-455 magic number nanoclusters of the photocatalyst and the increase of the reaction time, and the yield reaches a maximum value of 65 percent along with the continuous increase and the prolonging of the dosage of the catalyst.
As can be seen from the above examples and experimental examples, the CdSeS magic-number nanoclusters prepared by the method have a good photocatalytic effect on the photochemical reaction for preparing the amino acid derivative by reducing the imidic ester. The invention provides a low-cost choice for the synthesis of amino acid derivatives and has good application prospect.

Claims (10)

1. A CdSeS phantom nanocluster characterized by: the cadmium-selenium-containing sulfur-bearing material is prepared from a cadmium source, a selenium-containing raw material and a sulfur-containing raw material, wherein the molar ratio of Cd, Se to S in the raw material is 20: (5-10): (1-5);
the cadmium source is one or a mixture of cadmium tetradecanoate and cadmium oleate; the selenium-containing raw material is selected from one or a mixture of two or more of selenium powder, a CdSe induction period sample and a CdSe magic number nanocluster; the sulfur-containing raw material is selected from one or a mixture of two of sulfur powder and a CdS induction phase sample.
2. The CdSeS phantom nanocluster of claim 1, wherein: the selenium-containing raw material is selenium powder, and the sulfur-containing raw material is sulfur powder.
3. The CdSeS phantom nanocluster of claim 2, wherein: the reaction conditions for preparing the CdSeS magic-number nanoclusters are as follows: the temperature is 230 ℃ and 250 ℃, the time is 30-180 minutes, and the solvent is 1-octadecene.
4. The CdSeS phantom nanocluster according to claim 3, wherein: the reaction conditions for preparing the CdSeS magic-number nanoclusters are as follows: the temperature was 230 ℃ for 60 minutes.
5. The CdSeS phantom nanocluster of claim 1, wherein: the feeding ratio of the cadmium source to the selenium-containing raw material to the sulfur-containing raw material meets the condition that the molar ratio of Cd to Se to S is 20: 5: 2.5.
6. use of the CdSeS magic nanoclusters of any one of claims 1 to 5 as a photocatalyst.
7. A method for preparing amino acid derivatives, which is characterized in that: imine compound A and alkyl active ester B are subjected to photochemical reaction under the action of blue light and a photocatalyst to generate amino acid derivatives, and the reaction formula is as follows:
Figure FDA0003700768600000011
wherein R is 1 、R 2 Are each independently selected from C 1 -C 10 Alkyl groups of (a);
the photocatalyst is the CdSeS magic-number nanocluster as defined in any one of claims 1-5.
8. The method of claim 7, wherein: the reaction formula is as follows:
Figure FDA0003700768600000021
9. the method of claim 7, wherein: in the photochemical reaction, the dosage ratio of the photocatalyst, the imine compound A and the alkyl active ester B is (5-200 mg): 0.5 mmol: (0.5-3mmol), or the photochemical reaction is carried out for 4-8 h.
10. The method of claim 7, wherein: the photochemical reaction is carried out under the action of alkali, and the alkali is one or a mixture of two or more of potassium carbonate, potassium phosphate, monopotassium phosphate, cesium carbonate or pyridine;
and/or the photochemical reaction is carried out under the action of a reducing agent, wherein the reducing agent is one or a mixture of two or more of 2, 6-dimethyl-1, 4-dihydro-3, 5-pyridinedicarboxylic acid diethyl ester, N-diisopropylethylamine, triethylamine and 1, 8-diazabicycloundecen-7-ene;
and/or the photochemical reaction is carried out in a solvent, wherein the solvent is one or a mixture of two or more of dichloromethane, 1, 2-dichloroethylene, dimethyl sulfoxide, N-dimethylformamide or acetonitrile.
CN202210688800.1A 2022-06-17 2022-06-17 CdSeS phantom number nanocluster and application thereof as photocatalyst Active CN115007177B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210688800.1A CN115007177B (en) 2022-06-17 2022-06-17 CdSeS phantom number nanocluster and application thereof as photocatalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210688800.1A CN115007177B (en) 2022-06-17 2022-06-17 CdSeS phantom number nanocluster and application thereof as photocatalyst

Publications (2)

Publication Number Publication Date
CN115007177A true CN115007177A (en) 2022-09-06
CN115007177B CN115007177B (en) 2023-06-23

Family

ID=83075760

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210688800.1A Active CN115007177B (en) 2022-06-17 2022-06-17 CdSeS phantom number nanocluster and application thereof as photocatalyst

Country Status (1)

Country Link
CN (1) CN115007177B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115888841A (en) * 2023-01-06 2023-04-04 四川大学 Organic amine coordination CdSe nanosheet and application thereof as photocatalyst

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020146742A1 (en) * 1997-05-27 2002-10-10 Wybourne Martin N. Scaffold-organized metal, alloy, semiconductor and/or magnetic clusters and electronic devices made using such clusters
US20060231487A1 (en) * 2005-04-13 2006-10-19 Bartley Stuart L Coated filter media
US20110049442A1 (en) * 2009-03-31 2011-03-03 Schreuder Michael A Surface structures for enhancement of quantum yield in broad spectrum emission nanocrystals
EP2679538A1 (en) * 2012-06-25 2014-01-01 King Saud University Single-sized II-VI semiconductor nanocrystals, a method for the preparation thereof and their use in clinical light therapy
CN103599799A (en) * 2013-10-29 2014-02-26 江苏大学 Preparation method of CdSe/CdS core-shell structured quantum dot photocatalyst and application thereof
CN105885847A (en) * 2016-04-08 2016-08-24 武汉理工大学 Cadmium sulphide selenide solid solution quantum dot and preparation method and photocatalytic hydrogen production application thereof
US20180186639A1 (en) * 2015-07-25 2018-07-05 Sichuan University Method for preparation of magic-sized nano-crystalline substance
CN110651019A (en) * 2017-05-23 2020-01-03 默克专利股份有限公司 Method for synthesizing semiconductor nano-sized material
CN110759375A (en) * 2018-07-25 2020-02-07 四川大学 Preparation method of magic number cluster nanocrystalline
CN112567020A (en) * 2018-03-06 2021-03-26 埃皮博恩股份有限公司 Injectable ready-to-use cartilage, tendon and ligament repair compositions and methods of use thereof
CN113046083A (en) * 2021-03-16 2021-06-29 四川大学 Luminous magic number nanocluster, and preparation method and application thereof
CN113195487A (en) * 2018-10-12 2021-07-30 杭州多禧生物科技有限公司 2, 3-diaminosuccinyl conjugate linkers
US20220161247A1 (en) * 2019-03-22 2022-05-26 Oxford University Innovation Limited Photocatalyst

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020146742A1 (en) * 1997-05-27 2002-10-10 Wybourne Martin N. Scaffold-organized metal, alloy, semiconductor and/or magnetic clusters and electronic devices made using such clusters
US20060231487A1 (en) * 2005-04-13 2006-10-19 Bartley Stuart L Coated filter media
US20110049442A1 (en) * 2009-03-31 2011-03-03 Schreuder Michael A Surface structures for enhancement of quantum yield in broad spectrum emission nanocrystals
EP2679538A1 (en) * 2012-06-25 2014-01-01 King Saud University Single-sized II-VI semiconductor nanocrystals, a method for the preparation thereof and their use in clinical light therapy
CN103599799A (en) * 2013-10-29 2014-02-26 江苏大学 Preparation method of CdSe/CdS core-shell structured quantum dot photocatalyst and application thereof
US20180186639A1 (en) * 2015-07-25 2018-07-05 Sichuan University Method for preparation of magic-sized nano-crystalline substance
CN105885847A (en) * 2016-04-08 2016-08-24 武汉理工大学 Cadmium sulphide selenide solid solution quantum dot and preparation method and photocatalytic hydrogen production application thereof
CN110651019A (en) * 2017-05-23 2020-01-03 默克专利股份有限公司 Method for synthesizing semiconductor nano-sized material
CN112567020A (en) * 2018-03-06 2021-03-26 埃皮博恩股份有限公司 Injectable ready-to-use cartilage, tendon and ligament repair compositions and methods of use thereof
CN110759375A (en) * 2018-07-25 2020-02-07 四川大学 Preparation method of magic number cluster nanocrystalline
CN113195487A (en) * 2018-10-12 2021-07-30 杭州多禧生物科技有限公司 2, 3-diaminosuccinyl conjugate linkers
US20220161247A1 (en) * 2019-03-22 2022-05-26 Oxford University Innovation Limited Photocatalyst
CN113046083A (en) * 2021-03-16 2021-06-29 四川大学 Luminous magic number nanocluster, and preparation method and application thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DZHAGAN, V等: "Vibrational Raman spectra of CdSxSe1-x magic-size nanocrystals", 《PHYSICA STATUS SOLIDI-RAPID RESEARCH LETTERS》, pages 250 - 252 *
WANG, P等: "Magic-sized CdSe nanoclusters for efficient visible-light-driven hydrogen evolution", 《NANO RESEARCH》, pages 3106 - 3113 *
刘忠范等: "分解幻数团簇前驱体化合物低温制备高产率超小尺寸硫化镉量子点", 《物理化学学报》, pages 27 - 29 *
刘新梅: "Ⅱ-Ⅵ族半导体量子点的规模化合成及其光伏器件研究", 《中国博士学位论文全文数据库》, pages 014 - 5 *
朱婷婷等: "胶体硫化镉半导体幻数量子点F311的形成", 《中国化学会第30届学术年会摘要集-第三十六分会：纳米材料合成与组装》, pages 29 *
王坤等: "CdTe魔尺寸纳米晶的合成及其生长机理研究", 《工程科学与技术》, pages 213 - 219 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115888841A (en) * 2023-01-06 2023-04-04 四川大学 Organic amine coordination CdSe nanosheet and application thereof as photocatalyst

Also Published As

Publication number Publication date
CN115007177B (en) 2023-06-23

Similar Documents

Publication Publication Date Title
CN107051585A (en) A kind of composite catalyst and its application with high-efficiency photocatalysis oxidization
CN115007177A (en) CdSeS magic number nanocluster and application thereof as photocatalyst
CN111036272A (en) C3N4/LaVO4Composite photocatalyst and preparation method thereof
CN112047868B (en) Preparation method of aryl selenocyanate compound
Gao et al. Visible-light-induced decarboxylation/defluorosilylation protocol for synthesis of gem-difluoroalkenes
CN112547125B (en) CdS/NiPc photocatalyst for water photolysis and preparation method thereof
CN112877064A (en) Preparation method of pure Cs4PbBr6 perovskite quantum dot and product thereof
CN115888841B (en) Organic amine coordinated CdSe nano sheet and application thereof as photocatalyst
CN112058291A (en) Microspherical composite visible-light-driven photocatalyst and rapid preparation method and application thereof
CN114262610B (en) Preparation method of green carbon dot-based fluorescent powder
CN114702466B (en) Organic selenium compound and preparation method thereof
CN114507109B (en) Method for synthesizing bibenzyl compound by photocatalysis
CN113680364B (en) Meta-aminophenylboronic acid doped graphite-phase carbon nitride photocatalyst, preparation method and application thereof
CN113307831B (en) Preparation method and application of cobalt (II) coumarin Schiff base complex
CN107185521A (en) A kind of catalysis material and preparation method thereof
CN113522273A (en) Preparation method of oxygen vacancy-rich tungsten trioxide and application of oxygen vacancy-rich tungsten trioxide in photocatalytic reaction
CN118543361B (en) Oxygen vacancy doped nano rod composite material and preparation method and application thereof
CN116162458B (en) Method for regulating forming path of magic cluster/quantum dot and application of method for preparing magic cluster and quantum dot
CN116747885B (en) ZIF-67-derived CsPbBr3/Co3O4Preparation method and application of composite photocatalyst
CN116639650B (en) Method and system for decomposing water by photocatalysis by utilizing nonlinear spectrum conversion
CN115650952B (en) Microwave synthesis method of 5, 6-dihydro-cyclopenta [ B ] thiophene-4-ketone
CN111892630B (en) Organic iridium metal complex and preparation method and application thereof
CN112724374B (en) Preparation of novel conjugated microporous polymer based on boron-containing fluorescent dye and photocatalytic application of novel conjugated microporous polymer
CN114591724B (en) CdSe quantum dot luminescence property regulation and control method
CN118048149A (en) Method for preparing fluorescent carbon dots with high fluorescence quantum efficiency and narrow luminous peak half-peak width and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant