Non-noble metal / semiconductor core-shell nanoparticle composite structure and preparation method thereof

Abstract

The invention discloses a non-noble metal / semiconductor core-shell nanoparticle composite structure and a preparation method thereof, the non-noble metal / semiconductor core-shell nanoparticle composite structure comprises a non-noble metal / semiconductor core-shell nanoparticle composite structure body, and the core-shell nanoparticle composite structure body comprises an external structure and an internal structure; the external structure is a low-dimensional semiconductor material, and the internal structure is non-noble metal nanoparticles; the low-dimensional semiconductor and the non-noble metal nanoparticles jointly form a non-noble metal / semiconductor core-shell nanoparticle composite structure body. The core-shell nanoparticle composite structure designed by the invention not only can introduce'stress' and'defects' into a semiconductor catalyst material, but also can couple semiconductor photocatalysis and a metal plasmon effect to realize collaborative conversion of light energy-electric energy / heat energy.

Description

Technical Field

[0001] The present invention relates to the technical field of new energy materials, and particularly relates to a core-shell nanoparticle composite structure of a non-precious metal / semiconductor, and also relates to a preparation method of the core-shell nanoparticle composite structure of the non-precious metal / semiconductor. Background Art

[0002] With the increasingly severe energy crisis and environmental problems, the development of efficient light energy conversion materials has become an important research direction for solving energy problems. At present, traditional light energy conversion materials have problems such as high cost, poor stability, and limited light absorption ability, which limit their popularization in practical applications. The broadband absorption photo-thermal-electric conversion material based on the composite of non-precious metals and semiconductors has become a research hotspot due to its low cost and excellent performance. However, in the prior art, the design of the core-shell structure is not yet mature, and how to optimize the structure and improve the performance of the material still needs further research. Summary of the Invention

[0003] The object of the present invention is to provide a core-shell nanoparticle composite structure of a non-precious metal / semiconductor and a preparation method. The designed core-shell nanoparticle composite structure of the non-precious metal / semiconductor reduces the reflectivity and transmittance, improves the broadband absorption efficiency, realizes the coupling of photocatalysis and plasmon effect, and effectively improves the conversion efficiency of light energy to heat energy or electrical energy.

[0004] To achieve the above functions, the present invention designs a core-shell nanoparticle composite structure of a non-precious metal / semiconductor, including the main body of the core-shell nanoparticle composite structure of the non-precious metal / semiconductor. The main body of the core-shell nanoparticle composite structure of the non-precious metal / semiconductor is composed of an external structure and an internal structure. The external structure entirely wraps the internal structure, wherein the external structure is a low-dimensional semiconductor material, and the internal structure is a non-precious metal nanoparticle.

[0005] As a preferred technical solution of the present invention: the non-precious metal nanoparticle includes an outer passivation layer and a metal core, and the outer passivation layer covers the surface of the metal core.

[0006] As a preferred technical solution of the present invention: the metal core includes one of aluminum, iron, manganese, copper, zinc, chromium, nickel, vanadium, zirconium, tin, rare earth metals, and alkaline earth metals.

[0007] As a preferred technical solution of the present invention: the low-dimensional semiconductor material includes one of molybdenum disulfide, tungsten disulfide, aluminum sulfide, indium gallium phosphide, and cadmium telluride.

[0008] The present invention also designs a preparation method of the core-shell nanoparticle composite structure of the non-precious metal / semiconductor, and performs the following steps S1-S4 to complete the preparation of the core-shell nanoparticle composite structure of the non-precious metal / semiconductor:

[0009] Step S1: Prepare the metal core of the non-noble metal nanoparticles using the electro-explosion process;

[0010] Step S2: Prepare the outer passivation layer on the surface of the metal core by natural oxidation method;

[0011] Step S3: Prepare the low-dimensional semiconductor material on the surface of the outer passivation layer of the non-noble metal nanoparticles by hydrothermal reaction in an air atmosphere;

[0012] Step S4: Wash, centrifuge, and dry the solution after the hydrothermal reaction in Step S3 with deionized water, ethanol, and acetone respectively, and finally obtain the core-shell nanoparticle composite structure of non-noble metal / semiconductor.

[0013] As a preferred technical solution of the present invention: The explosion process of the electro-explosion process described in Step S1 includes the following stages: solid-state heating, melting, liquid heating, gasification expansion, and arc breakdown.

[0014] Beneficial effects: Compared with the prior art, the advantages of the present invention include:

[0015] 1. High-efficiency light energy conversion:

[0016] Through the coupling of the non-noble metal core and the low-dimensional semiconductor shell, the material exhibits strong absorption ability in a wide spectral range, realizing high-efficiency light energy conversion;

[0017] 2. Low cost and high stability:

[0018] Compared with noble metal catalysts, using non-noble metals such as Al as the core significantly reduces the material cost, and at the same time improves the structural stability through the Al 2 O 3 passivation layer;

[0019] 3. Multifunctional application potential:

[0020] This material is not only suitable for the field of photocatalysis, but also can play a role in photothermal conversion, photoelectric detection, and new energy devices, and has broad application prospects. Brief description of the drawings

[0021] Figure 1 is a schematic diagram of the hierarchical structure of the core-shell nanoparticle composite structure of non-noble metal / semiconductor provided by an embodiment of the present invention;

[0022] Figure 2 is a schematic diagram of the preparation process of the core-shell nanoparticle composite structure of non-noble metal / semiconductor provided by an embodiment of the present invention;

[0023] Figure 3SEM characterization diagram and particle size distribution diagram of the non-precious metal / semiconductor core-shell nanoparticle composite structure provided by an embodiment of the present invention;

[0024] Figure 4 TEM characterization diagram of the non-precious metal / semiconductor core-shell nanoparticle composite structure provided by an embodiment of the present invention;

[0025] Figure 5 Spectral absorption diagram of the non-precious metal / semiconductor core-shell nanoparticle composite structure provided by an embodiment of the present invention. Detailed implementation manners

[0026] The present invention will be further described below with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solutions of the present invention and cannot be used to limit the protection scope of the present invention.

[0027] The non-precious metal / semiconductor core-shell nanoparticle composite structure provided by an embodiment of the present invention, referring to Figure 1 , includes a non-precious metal / semiconductor core-shell nanoparticle composite structure body, which is composed of an external structure and an internal structure. The external structure entirely wraps the internal structure, where the external structure is a low-dimensional semiconductor material and the internal structure is a non-precious metal nanoparticle.

[0028] The non-precious metal nanoparticle includes an outer passivation layer and a metal inner core, and the outer passivation layer covers the surface of the metal inner core.

[0029] The metal inner core includes one of aluminum (Al), iron (Fe), manganese (Mn), copper (Cu), zinc (Zn), chromium (Cr), nickel (Ni), vanadium (V), zirconium (Zr), tin (Sn), rare earth metals, and alkaline earth metals.

[0030] The low-dimensional semiconductor material includes one of molybdenum disulfide (MoS 2 ), tungsten disulfide (WS 2 ), aluminum sulfide (Al 2 S 3 ), indium gallium phosphide (InGaP), and cadmium telluride (CdTe).

[0031] The embodiment of the present invention also provides a preparation method for the non-precious metal / semiconductor core-shell nanoparticle composite structure. Referring to Figure 2 , perform the following steps S1-S4 to complete the preparation of the non-precious metal / semiconductor core-shell nanoparticle composite structure:

[0032] Step S1: Use an electro-explosion process to prepare the metal inner core of the non-precious metal nanoparticle;

[0033] The explosion process of the electro-explosion process includes the following stages: solid-state heating, melting, liquid heating, vaporization expansion, and arc breakdown.

[0034] Step S2: Prepare an outer passivation layer on the surface of the metal core by natural oxidation method;

[0035] Step S3: Prepare a low-dimensional semiconductor material on the surface of the outer passivation layer of the non-precious metal nanoparticles by hydrothermal reaction in an air atmosphere;

[0036] Step S4: Wash, centrifuge, and dry the solution after the hydrothermal reaction in Step S3 with deionized water, ethanol, and acetone respectively, and finally obtain a core-shell nanoparticle composite structure of non-precious metal / semiconductor.

[0037] In one embodiment, the metal core material of the non-precious metal nanoparticles is Al, and the outer passivation layer of the non-precious metal nanoparticles is Al 2 O 3 , and the low-dimensional semiconductor material is MoS 2 ; The preparation steps of the core-shell nanoparticle composite structure of non-precious metal / semiconductor are as follows:

[0038] Step S1: Core preparation:

[0039] Prepare Al nanoparticles with a particle size of 50 nm by electro-explosion process. The electro-explosion process includes five stages: solid-state heating, melting, liquid heating, vaporization expansion, and arc breakdown, and finally form Al nanoparticles with a particle size of 50 nm;

[0040] Step S2: Outer passivation layer preparation:

[0041] Naturally oxidize on the surface of the Al nano-core to form a stable Al 2 O 3 passivation layer. Through the natural oxidation method, a uniform Al 2 O 3 passivation layer is formed in the air environment to prevent further oxidation of the Al metal core;

[0042] Step S3: Outer shell growth:

[0043] React with ammonium tetrathiomolybdate at 195 °C for 10 hours by hydrothermal method to form a few-layer MoS 2 shell layer outside the core-shell structure.

[0044] Step S4: Wash, centrifuge, and dry the solution after the hydrothermal reaction in Step S3 with deionized water, ethanol, and acetone respectively, and finally obtain a core-shell nanoparticle composite structure of non-precious metal / semiconductor.

[0045] The core-shell nanoparticle composite structure of non-noble metal / semiconductor prepared by the present invention has the performance of strong absorption in a wide spectrum, and can effectively capture visible light and near-infrared light in sunlight; the plasmonic effect coupling of low-dimensional semiconductor and non-noble metal core significantly improves the photo-thermal-electric conversion efficiency; the "stress" and "defects" introduced on the material surface further optimize the photocatalytic performance.

[0046] The SEM characterization diagram and particle size distribution diagram of the core-shell nanoparticle composite structure of non-noble metal / semiconductor prepared by the present invention are referred to Figure 3 , the absorption spectrum of the core-shell nanoparticle composite structure of non-noble metal / semiconductor prepared in this example was tested by using a transmission electron microscope (TEM), and the TEM characterization diagram is referred to Figure 4 , and the spectral absorption diagram is referred to Figure 5 , the absorption rate of the incident light of the material prepared in this example is higher than 70% in the wavelength range of 400 nm to 2000 nm, and the sunlight absorption rate reaches 90% in the wavelength range of 1500 nm to 2000 nm. At present, there is no prior art with a sunlight absorption rate greater than 90% in the full wavelength range of 200 nm to 2500 nm, and there is also no prior art with a sunlight absorption rate exceeding 93% in the wavelength range of 200 nm to 2500 nm.

[0047] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those of ordinary skill in the art.

Claims

1. A non-precious metal / semiconductor core-shell nanoparticle composite structure, characterized in that: It includes a non-precious metal / semiconductor core-shell nanoparticle composite structure body, which is composed of an external structure and an internal structure. The external structure as a whole wraps the internal structure, wherein the external structure is a low-dimensional semiconductor material and the internal structure is non-precious metal nanoparticles.

2. The non-noble metal / semiconductor core-shell nanoparticle composite structure according to claim 1, characterized in that: The non-precious metal nanoparticles include an outer passivation layer and a metal core, wherein the outer passivation layer covers the surface of the metal core.

3. The non-noble metal / semiconductor core-shell nanoparticle composite structure according to claim 1, characterized in that: The metal core includes one of aluminum, iron, manganese, copper, zinc, chromium, nickel, vanadium, zirconium, tin, rare earth metals and alkaline earth metals.

4. The non-noble metal / semiconductor core-shell nanoparticle composite structure according to claim 1, characterized in that: The low-dimensional semiconductor material includes one of molybdenum disulfide, tungsten disulfide, aluminum sulfide, gallium indium phosphide, and cadmium telluride.

5. A method for preparing a non-precious metal / semiconductor core-shell nanoparticle composite structure, characterized in that: Perform the following steps S1 to S4 to complete the preparation of the non-noble metal / semiconductor core-shell nanoparticle composite structure as described in any one of claims 1 to 5: Step S1: preparing a metal core of non-precious metal nanoparticles by using an electric explosion process; Step S2: preparing an outer passivation layer on the surface of the metal core by a natural oxidation method; Step S3: preparing a low-dimensional semiconductor material on the surface of the outer passivation layer of the non-noble metal nanoparticles by a hydrothermal reaction in an air atmosphere; Step S4: The solution after the hydrothermal reaction in step S3 is washed and centrifuged with deionized water, ethanol and acetone respectively, and dried to finally obtain a non-precious metal / semiconductor core-shell nanoparticle composite structure.

6. The method for preparing a non-noble metal / semiconductor core-shell nanoparticle composite structure according to claim 5, characterized in that: The explosion process of the electric explosion process described in step S1 includes the following stages: solid state heating, melting, liquid state potential addition, gasification expansion, and arc breakdown.

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