CN111974421B - Preparation method of metal/semiconductor heterojunction composite material with efficient interface charge transfer - Google Patents
Preparation method of metal/semiconductor heterojunction composite material with efficient interface charge transfer Download PDFInfo
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- 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
-
- B01J35/39—
-
- B01J35/40—
-
- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a metal/semiconductor heterojunction composite material with efficient interface charge transfer. The CdSe @ Pd nano composite material which is stable at room temperature and has high-efficiency interface charge transfer is prepared by firstly synthesizing CdSe quantum dots with negative charges by a solvothermal method, extracting by an organic reduction method to obtain Pd @ DMAP colloidal solution with positive charges and then by a simple electrostatic self-assembly method. The nano composite material has reducibility and stability obviously superior to those of a single-component semiconductor (CdSe) under the irradiation of visible light (lambda is greater than 420 nm) with isocandela intensity, can be used for catalytic reduction of p-nitroaniline, has a simple preparation process, is green and environment-friendly, and is beneficial to sustainable development of environment and energy.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a metal/semiconductor heterojunction composite material with efficient interface charge transfer.
Background
In recent years, the field of photocatalysis has wide application prospect in the fields of photocatalytic hydrogen production, selective photooxidation reduction, organic pollutant degradation reaction and the like due to the green and pollution-free property, and is expected to be concerned about solving the energy and environment crisis. The nanometer function integrated composite material with a specific structure overcomes the defects of single-component nanometer particles, can organically combine multiple functions of different substances together, and shows superior performance which cannot be achieved by common single-component nanometer particles, so that the nanometer function integrated composite material is widely applied to various fields, such as photoelectrochemistry, quantum dots, sensors, catalysis and the like.
Among them, the zero-dimensional nano-semiconductor CdSe quantum dot has unique structural advantages including larger specific surface area and pore volume, stronger light absorption/scattering, light stability and its unique quantum size effect, compared with the conventional nanorods, nanowires and bulk materials. However, electron holes excited by the CdSe quantum dot matrix are easy to recombine and generate unnecessary agglomeration, which is not beneficial to the quick and effective charge transmission of photon-generated carriers and the space separation of photon-generated electron hole pairs, so that the excited photon-generated electron holes can not effectively participate in the photooxidation-reduction reaction, and the application of the photocatalysis of the CdSe quantum dots is limited.
Disclosure of Invention
The invention aims to provide a static self-assembly preparation method of a metal/semiconductor heterojunction composite material with efficient interface charge transfer, aiming at the problems that the catalytic performance of the existing single semiconductor component is insufficient and the procedure for synthesizing the composite material is complex under most conditions.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a metal/semiconductor heterojunction composite material with efficient interface charge transfer is characterized by firstly utilizing a solvothermal method to synthesize CdSe quantum dots with negative charges, adopting an organic reduction method to extract to obtain Pd @ DMAP colloidal solution with positive charges, and then preparing the CdSe @ Pd nano composite material which is stable at room temperature and has efficient interface charge transfer by an electrostatic self-assembly method; the method specifically comprises the following steps:
(1) Preparation of CdSe quantum dots:
CdCl of 2 mmol/L at 200 mL 2 ·2.5H 2 Continuously introducing nitrogen into the water solution of O, continuously stirring to sufficiently remove oxygen dissolved in water, then adding 230 mu L of thioglycolic acid (MAA) as a stabilizer, stirring vigorously for 2h, and adjusting the pH value to 11 by using a NaOH solution with the concentration of 1 mol/L; another 0.632g of NaBH 4 Dissolving in 10mL of deionized water, adding 0.2106g of selenium powder, stirring in an ice bath at a low speed for 2 hours, and continuously introducing nitrogen to prevent oxidation to prepare an oxygen-free NaHSe aqueous solution; 5mL of freshly prepared NaHSe aqueous solution was then rapidly injected into the CdCl 2 ·2.5H 2 Changing the solution into orange red in an O aqueous solution, vigorously stirring and refluxing at 80 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, adding ethanol with the same volume, vigorously stirring for 1 hour, standing, washing the precipitate with ethanol for 3-5 times, centrifuging, and drying (vacuum drying at the temperature of 50-70 ℃) to obtain the CdSe quantum dots;
(2) Preparation of pd @ dmap colloidal solution:
80ml of toluene and 30 mL, 30 mmol/L of Na are added 2 PdCl 4 The solution was mixed and stirred until the color changed from colorless to dark brown, then 25 mL freshly prepared NaBH of 0.4 mol/L concentration was added 4 The solution turns black, is vigorously stirred for 30 minutes to reduce the solution into metal nano crystals of Pd, and after the two phases are separated, the solution is sequentially added with 0.1 mol/L H 2 SO 4 Washing the solution, 0.1 mol/L NaOH solution and deionized water once, and adding excessive anhydrous Na 2 SO 4 Drying; then adding 80mL and 0.1 mol/L4-dimethyl ammonia into the obtained Pd nano crystal solutionDirectly standing a pyridine (DMAP) aqueous solution for 2 hours without stirring, and then separating out a water phase to obtain a Pd @ DMAP colloidal solution;
(3) Preparation of CdSe @ Pd nanocomposite:
taking 5mL of Pd @ DMAP colloidal solution, adjusting the pH of the colloidal solution to 10 (adjusting by adopting 3 mol/L hydrochloric acid solution and 3 mol/L sodium hydroxide solution), then adding the colloidal solution into 20 mL and 1 mg/mL CdSe quantum dot aqueous solution with the same pH of 10, violently stirring for 1 hour to enable Pd nanocrystals to be fully adsorbed on the CdSe quantum dots, and then centrifuging and drying (vacuum drying, the temperature is 50-70 ℃) to obtain the CdSe @ Pd nano composite material with efficient interface charge transfer.
The CdSe @ Pd nano composite material prepared by the invention can be used for catalytic reduction of paranitroaniline.
The invention has the following remarkable advantages:
(1) The preparation method has short period, is environment-friendly and easy to recover, and is beneficial to the sustainable development of environment and energy;
(2) The invention is synthesized by a simple positive and negative charge electrostatic self-assembly method, has simple and efficient process operation, and is beneficial to large-scale and industrial production;
(3) The nano composite material synthesized by the method has high photocatalytic activity and selectivity and good cycle performance, and solves the problem of limitation of the use of a single-component CdSe quantum dot semiconductor catalyst.
According to the invention, the precious metal Pd modified by a surface ligand DMAP is introduced into the CdSe quantum dots, and the lower Fermi level of the precious metal Pd can be used for rapidly capturing photo-generated electrons to promote the transfer of interface charges, so that the effect of prolonging the service life of photo-generated carriers is achieved; meanwhile, the photoproduction holes left on the valence band after the quantum dots are excited can participate in a series of oxidation reactions, so that the effective utilization rate of energy is improved; and the loading of the noble metal can greatly enhance the light absorption capability of the semiconductor to promote more efficient solar energy conversion. Therefore, the simple, green and efficient preparation method of the metal/semiconductor heterojunction composite material has profound significance and wide application prospect in the technical field of material preparation and the field of selective organic synthesis.
Drawings
FIG. 1 is a Zeta potential diagram of the CdSe quantum dots prepared by the example;
FIG. 2 is a Zeta potential diagram of Pd @ DMAP prepared in example;
FIG. 3 is a scanning electron micrograph of CdSe quantum dots prepared by the example;
FIG. 4 is a scanning electron micrograph of a CdSe @ Pd nanocomposite prepared by the example;
FIG. 5 is a transmission electron microscope image of the CdSe quantum dots and CdSe @ Pd nanocomposite prepared by the example;
FIG. 6 is a comparison graph of the reduction performance of CdSe quantum dots prepared in examples and CdSe @ Pd paranitroaniline with different loading amounts.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Examples
A three-necked flask was charged with 200 mL, 2 mmol/L CdCl 2 ·2.5H 2 Continuously introducing nitrogen into the O aqueous solution, continuously stirring to sufficiently remove oxygen dissolved in water, then adding 230 mu L of MAA, stirring vigorously for 2h, and adjusting the pH value to 11 by using a NaOH solution with the concentration of 1 mol/L; another 0.632g of NaBH 4 Dissolving in 10mL of deionized water, adding 0.2106g of selenium powder, stirring in an ice bath at a low speed for 2 hours, and continuously introducing nitrogen to prevent oxidation to prepare an oxygen-free NaHSe aqueous solution; 5mL of freshly prepared NaHSe aqueous solution was then rapidly injected into the CdCl 2 ·2.5H 2 Changing the solution into orange red in an O aqueous solution, carrying out violent stirring reflux reaction for 4 hours at the temperature of 80 ℃, cooling to room temperature after the reaction is finished, adding ethanol with the same volume, carrying out violent stirring for 1 hour, standing for several hours, removing supernatant, washing the precipitate with ethanol for 3-5 times (40 mL each time), centrifuging, drying (vacuum drying at the temperature of 50-70 ℃) to obtain CdSe quantum dots;
all glassware was treated with aqua regia (HCl and HNO) 3 3:1) for 12 hours and using deionizationThoroughly washing with sub-water for 3-5 times; the washed glassware was dried and charged with 80ml of toluene and 30 mL, 30 mmol/L Na 2 PdCl 4 The solution was mixed and stirred until the color of the solution changed from colorless to dark brown, and then 25 mL freshly prepared NaBH of 0.4 mol/L concentration was added 4 The aqueous solution, which turned black, was vigorously stirred for 30 minutes, after separation of the two phases, with 0.1 mol/L H in succession 2 SO 4 Washing the solution, 0.1 mol/L NaOH solution and deionized water once, and adding excessive anhydrous Na 2 SO 4 Drying; then adding 80mL and 0.1 mol/L DMAP aqueous solution into the obtained Pd nano crystal solution, directly standing for 2 hours without stirring, and then separating out the water phase for dissolving Pd by using a separation funnel to obtain Pd @ DMAP colloidal solution;
adjusting the pH value of the Pd @ DMAP colloidal solution to 10 (adjusting by adopting 3 mol/L hydrochloric acid solution and 3 mol/L sodium hydroxide solution), adding different volumes (1, 3, 5, 7 and 10 mL) into 20 mL and 1 mg/mL CdSe quantum dot water solutions with the same pH value of 10, violently stirring for 1 hour, centrifuging and drying (vacuum drying at the temperature of 50-70 ℃) to obtain the CdSe @ Pd nano composite materials with different loading amounts.
Reduction Performance test
The CdSe @ Pd nano composite materials with different loading amounts of 10 mg are respectively dispersed in 40 ml of paranitroaniline solution with 5 ppm in an ultrasonic mode, dark adsorption is carried out for 30 minutes, nitrogen gas (80 mL/min) is continuously introduced, then the paranitroaniline solution is placed under visible light (> 420 nm) to be irradiated for 10 minutes, then a proper amount of liquid is taken, an ultraviolet visible light spectrometer is adopted to measure the content of the paranitroaniline in the liquid, the conversion rate is calculated, cdSe quantum dots are used for comparison, and the result is shown in figure 6. As can be seen from FIG. 6, the CdSe @5Pd nanocomposite prepared by adding 5mL of Pd @ DMAP has the best performance, and the conversion rate of paranitroaniline is about 94.4%.
The above description is only a preferred embodiment of the present invention, and all the equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.
Claims (6)
1. A preparation method of a metal/semiconductor heterojunction composite material for catalytic reduction of p-nitroaniline is characterized by comprising the following steps: synthesizing CdSe quantum dots with negative electricity by a solvothermal method, extracting by an organic reduction method to obtain Pd @ DMAP colloidal solution with positive electricity, and preparing the CdSe @ Pd nano composite material which is stable at room temperature and has high-efficiency interface charge transfer by an electrostatic self-assembly method; the method specifically comprises the following steps:
(1) Preparation of CdSe quantum dots:
CdCl at 200 mL, 2 mmol/L 2 ·2.5H 2 Continuously introducing nitrogen into the water solution of O, continuously stirring to sufficiently remove oxygen dissolved in water, then adding 230 mu L of thioglycolic acid as a stabilizer, stirring vigorously for 2 hours, and adjusting the pH value to 11 by using a NaOH solution; another 0.632g of NaBH 4 Dissolving in 10mL of deionized water, adding 0.2106g selenium powder, stirring in ice bath at low speed for 2h, and continuously introducing nitrogen to prevent oxidation to prepare an oxygen-free NaHSe aqueous solution; 5mL of freshly prepared NaHSe aqueous solution was then rapidly injected into the CdCl 2 ·2.5H 2 In the water solution of O, stirring vigorously at 80 ℃ for reflux reaction for 4h, cooling to room temperature after the reaction is finished, adding ethanol with the same volume, stirring vigorously for 1h, standing, washing the precipitate, and performing centrifugal drying to obtain CdSe quantum dots;
(2) Preparation of colloidal solution of Pd @ DMAP:
80ml of toluene and 30 mL, 30 mmol/L of Na are added 2 PdCl 4 The solution was mixed and stirred well and then 25 mL freshly prepared NaBH of 0.4 mol/L concentration was added 4 Stirring the aqueous solution vigorously for 30 min, separating the two phases, and sequentially adding H 2 SO 4 Washing the solution, naOH solution and deionized water once, and adding excessive anhydrous Na 2 SO 4 Drying; then adding 80mL and 0.1 mol/L DMAP aqueous solution into the obtained Pd nano crystal solution, standing for 2 hours, and then separating out a water phase to obtain Pd @ DMAP colloidal solution;
(3) Preparation of CdSe @ Pd nanocomposite:
taking 5mL Pd @ DMAP colloidal solution, adjusting the pH value to 10, then adding the colloidal solution into 20 mL and 1 mg/mL CdSe quantum dot water solution with the same pH value of 10, violently stirring for 1 hour, centrifuging and drying to obtain the CdSe @ Pd nano composite material with efficient interface charge transfer.
2. The method for preparing a metal/semiconductor heterojunction composite material as claimed in claim 1, wherein: the concentration of the NaOH solution used in the step (1) is 1 mol/L.
3. The method for preparing a metal/semiconductor heterojunction composite material as claimed in claim 1, wherein: the drying in the step (1) is vacuum drying, and the temperature is 50-70 ℃.
4. The method for preparing a metal/semiconductor heterojunction composite material according to claim 1, wherein: h used in the step (2) 2 SO 4 The concentration of the solution and the NaOH solution are both 0.1 mol/L.
5. The method for preparing a metal/semiconductor heterojunction composite material according to claim 1, wherein: in the step (3), a 3 mol/L hydrochloric acid solution and a 3 mol/L sodium hydroxide solution are adopted for adjusting the pH.
6. The method for preparing a metal/semiconductor heterojunction composite material as claimed in claim 1, wherein: the drying in the step (3) is vacuum drying, and the temperature is 50-70 ℃.
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| US9627200B2 (en) * | 2013-07-29 | 2017-04-18 | US Nano LLC | Synthesis of CdSe/ZnS core/shell semiconductor nanowires |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101906298A (en) * | 2010-08-13 | 2010-12-08 | 济南大学 | Surface plasma fluorescence-enhanced nano composite structure film and preparation method thereof |
| CN107754822A (en) * | 2017-10-27 | 2018-03-06 | 江苏大学 | A kind of preparation and its application based on CdSe/BiOCl composite photo-catalysts |
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