A preparation method of sub-nanometer-sized gallium oxide nanowires

Abstract

The present invention discloses a method for preparing gallium oxide nanowires with sub-nanometer size. The process is as follows: (1) Dissolve an inorganic gallium salt in a mixed solvent of an organic amine and an organic phosphine, and under an inert gas condition, stir and heat until it becomes clear; (2) Then transfer the mixed solvent into an autoclave, introduce an activation reagent, and react under solvothermal reaction conditions to obtain gallium oxide nanowires with sub-nanometer size. This synthesis method is simple to operate and has mild conditions; by using this method, high-quality gallium oxide nanowires with sub-nanometer size can be prepared, with a diameter of 1.0 ± 0.2 nm and a length of 200 - 300 nm, having the advantages of uniform morphology, uniform wire diameter, and good crystallinity; the obtained gallium oxide nanowires with sub-nanometer size have broad application values in optoelectronic devices, sensing detection, and the catalytic field.

Description

Technical Field

[0001] The present invention relates to the field of nanomaterial synthesis, and particularly to a method for preparing gallium oxide nanowires with sub-nanometer size. Background Art

[0002] Sub-nanometer sized semiconductor nanowires refer to semiconductor nanowires with a diameter close to or less than 1.0 nm and an aspect ratio greater than 30. Compared with conventional semiconductor nanowires (diameter > 10 nm), sub-nanometer sized semiconductor nanowires have important application potential in fields such as sensing detection, efficient catalysis, lighting display, etc. due to their strong anisotropic characteristics and significant quantum confinement effect.

[0003] Gallium oxide nanowires, as an extremely important wide-bandgap (> 4.9 eV) semiconductor material, are widely used in fields such as gas sensing and solar-blind photodetection due to their excellent optoelectronic properties and abundant surface oxygen defects. At present, researchers at home and abroad have successfully prepared conventional-sized gallium oxide nanowires using methods such as physical vapor deposition and template-assisted deposition. Unfortunately, there is currently no report on the preparation of sub-nanometer sized gallium oxide nanowires using a solvothermal strategy. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a method for preparing gallium oxide nanowires with sub-nanometer size using a solvothermal strategy.

[0005] To solve the above technical problem, the process adopted by the present invention is as follows:

[0006] (1) Dissolve an inorganic gallium salt in a mixed solvent of an organic amine and an organic phosphine, and under an inert gas condition, stir and heat to clarity;

[0007] (2) Then add an activation reagent to the mixed solvent, and react under an inert atmosphere and solvothermal reaction conditions to obtain sub-nanometer sized gallium oxide nanowires.

[0008] Further, in the step (1), the inorganic gallium salt is selected from one or more of gallium acetylacetonate, gallium chloride, gallium nitrate, and gallium sulfate; the organic amine is selected from one or more of hexylamine, octylamine, dodecylamine, hexadecylamine, and oleylamine; the organic phosphine is tri-n-octylphosphine, tri-n-butylphosphine, and / or tri-n-octylphosphine oxide.

[0009] Further, in the step (2), the activation reagent is sodium borohydride, lithium triethylborohydride, and / or tetrabutylammonium borohydride.

[0010] Further, in the step (2), the reaction is carried out under solvothermal reaction conditions of 80 - 200 °C for 0.5 - 10 h.

[0011] Further, in the step (1), 0.1 - 3.0 mmol of inorganic gallium salt is dissolved in a mixed solvent of 5.0 - 20 mL of organic amine and 5.0 - 20 mL of organic phosphine; in the step (2), 0.05 - 0.3 mL of an activating reagent is added.

[0012] The beneficial effects of adopting the above technical solution are as follows: The synthesis method of the present invention is simple in operation and mild in conditions; by using this method, high-quality gallium oxide nanowires with sub-nanometer size can be prepared, with a diameter of 1.0 ± 0.2 nm and a length of 200 - 300 nm, having the advantages of uniform morphology, uniform wire diameter, and good crystallinity; the obtained sub-nanometer size gallium oxide nanowires have wide application values in optoelectronic devices, sensing detection, and the catalytic field. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The present invention will be further described in detail below in conjunction with the drawings and specific embodiments.

[0014] Figure 1 It is a transmission electron microscope image of the sub-nanometer size gallium oxide nanowires obtained in Example 1 of the present invention;

[0015] Figure 2 It is an XRD spectrum of the sub-nanometer size gallium oxide nanowires obtained in Example 1 of the present invention;

[0016] Figure 3 It is a transmission electron microscope image of the sub-nanometer size gallium oxide nanowires obtained in Example 2 of the present invention;

[0017] Figure 4 It is a transmission electron microscope image of the sub-nanometer size gallium oxide nanowires obtained in Example 3 of the present invention;

[0018] Figure 5 It is a transmission electron microscope image of the sub-nanometer size gallium oxide nanowires obtained in Example 4 of the present invention;

[0019] Figure 6 It is a transmission electron microscope image of the sub-nanometer size gallium oxide nanowires obtained in Example 5 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0020] The process steps of the preparation method of the sub-nanometer size gallium oxide nanowires are as follows:

[0021] (1) Dissolve 0.1 - 3.0 mmol of inorganic gallium salt in a mixed solvent of 5.0 - 20 mL of organic amine and 5.0 - 20 mL of organic phosphine. Preferably, dissolve 0.5 - 1.5 mmol of inorganic gallium salt in a mixed solvent of 8 - 12 mL of organic amine and 8 - 12 mL of organic phosphine. Under inert gas conditions, stir and heat to clarity. The inorganic gallium salt is selected from one or more of gallium acetylacetonate, gallium chloride, gallium nitrate, and gallium sulfate. The organic amine is selected from one or more of hexylamine, octylamine, dodecylamine, hexadecylamine, and oleylamine. The organic phosphine is tri-n-octylphosphine, tri-n-butylphosphine, and / or tri-n-octylphosphine oxide.

[0022] (2) Then transfer the mixed solvent into an autoclave, add 0.05 - 0.30 mL of an activation reagent, preferably 0.05 - 0.15 mL of an activation reagent. Seal the high-pressure reaction kettle and react for 0.5 - 10 h under solvothermal reaction conditions at 80 - 200 °C in an inert atmosphere. Preferably, react for 4 - 8 h under solvothermal reaction conditions at 140 - 170 °C to obtain gallium oxide nanowires with sub-nanometer dimensions. The activation reagent is sodium borohydride, lithium triethylborohydride, and / or tetrabutylammonium borohydride. The diameter of the obtained gallium oxide nanowires with sub-nanometer dimensions is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

[0023] Example 1: The preparation method of the gallium oxide nanowires with sub-nanometer dimensions adopts the following specific process.

[0024] Dissolve 1.2 mmol of gallium acetylacetonate in a mixed solvent of 10 mL of oleylamine and 10 mL of tri-n-octylphosphine. Under inert gas conditions, stir and heat to clarity. Then transfer it into an autoclave, introduce 0.1 mL of lithium triethylborohydride, and react at 150 - 160 °C under solvothermal reaction conditions for 6 h in an inert atmosphere to obtain gallium oxide nanowires with sub-nanometer dimensions.

[0025] Figure 1 The transmission electron microscope image of the gallium oxide nanowires with sub-nanometer dimensions obtained in this example is shown; Figure 2 The XRD spectrum of the gallium oxide nanowires with sub-nanometer dimensions obtained in this example is shown. From Figure 1 、 Figure 2 It can be seen that the obtained gallium oxide nanowires with sub-nanometer dimensions are monoclinic, the diameter of the nanowires is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

[0026] Example 2: The preparation method of the gallium oxide nanowires with sub-nanometer dimensions adopts the following specific process.

[0027] Dissolve 1.0 mmol of gallium chloride in a mixed solvent of 12 mL of hexylamine and 9 mL of tri-n-octylphosphine. Under an inert gas condition, stir and heat until it becomes clear. Then transfer it into an autoclave, introduce 0.12 mL of sodium borohydride, and react at 160 - 170 °C under solvothermal reaction conditions for 4 h in an inert atmosphere to obtain sub-nanometer-sized gallium oxide nanowires. The sub-nanometer-sized gallium oxide nanowires obtained in this example are in the monoclinic crystal form. The diameter of the nanowires is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

[0028] Figure 3 is the transmission electron microscopy image of the sub-nanometer-sized gallium oxide nanowires obtained in this example. It can be Figure 3 seen that the obtained sub-nanometer-sized gallium oxide nanowires are in the monoclinic crystal form. The diameter of the nanowires is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

[0029] Example 3: The preparation method of this sub-nanometer-sized gallium oxide nanowire adopts the following specific process.

[0030] Dissolve 1.5 mmol of gallium acetylacetonate in a mixed solvent of 10 mL of dodecylamine and 12 mL of tri-n-butylphosphine. Under an inert gas condition, stir and heat until it becomes clear. Then transfer it into an autoclave, introduce 0.15 mL of sodium borohydride, and react at 150 - 160 °C under solvothermal reaction conditions for 8 h in an inert atmosphere to obtain sub-nanometer-sized gallium oxide nanowires. The sub-nanometer-sized gallium oxide nanowires obtained in this example are in the monoclinic crystal form. The diameter of the nanowires is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

[0031] Figure 4 The transmission electron microscopy image of the sub-nanometer-sized gallium oxide nanowires obtained in this example, it can be Figure 4 seen that the obtained sub-nanometer-sized gallium oxide nanowires are in the monoclinic crystal form. The diameter of the nanowires is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

[0032] Example 4: The preparation method of this sub-nanometer-sized gallium oxide nanowire adopts the following specific process.

[0033] Dissolve 0.5 mmol of gallium nitrate in a mixed solvent of 8 mL of octylamine and 8 mL of tri-n-butylphosphine. Under an inert gas condition, stir and heat until it becomes clear. Then transfer it into an autoclave, introduce 0.05 mL of lithium triethylborohydride, and react at 140 - 150 °C under solvothermal reaction conditions for 7 h to obtain sub-nanometer-sized gallium oxide nanowires.

[0034] Figure 5 The transmission electron microscopy image of the sub-nanometer-sized gallium oxide nanowires obtained in this example, it can be Figure 5It can be seen that the obtained gallium oxide nanowires with sub-nanometer size are monoclinic. The diameter of the nanowires is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

[0035] Example 5: The preparation method of the sub-nanometer size gallium oxide nanowires adopts the following specific process.

[0036] Dissolve 0.1 mmol of gallium sulfate in a mixed solvent of 5 mL of hexadecylamine and 5 mL of tri-n-octylphosphine oxide. Under the condition of inert gas, stir and heat until it becomes clear. Then transfer it into an autoclave, and introduce 0.08 mL of tetrabutylammonium borohydride. React under solvothermal reaction conditions of 190 - 200 °C for 0.5 h under an inert atmosphere, and sub-nanometer size gallium oxide nanowires can be obtained.

[0037] Figure 6 The transmission electron microscope image of the sub-nanometer size gallium oxide nanowires obtained in this example is shown by Figure 6 It can be seen that the obtained gallium oxide nanowires with sub-nanometer size are monoclinic. The diameter of the nanowires is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

[0038] Example 6: The preparation method of the sub-nanometer size gallium oxide nanowires adopts the following specific process.

[0039] Dissolve 2.0 mmol of gallium acetylacetonate in a mixed solvent of 12 mL of dodecylamine and 20 mL of tri-n-butylphosphine. Under the condition of inert gas, stir and heat until it becomes clear. Then transfer it into an autoclave, and introduce 0.20 mL of sodium borohydride. React under solvothermal reaction conditions of 80 - 90 °C for 10 h under an inert atmosphere, and sub-nanometer size gallium oxide nanowires can be obtained. The sub-nanometer size gallium oxide nanowires obtained in this example are monoclinic. The diameter of the nanowires is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

[0040] Example 7: The preparation method of the sub-nanometer size gallium oxide nanowires adopts the following specific process.

[0041] Dissolve 3.0 mmol of gallium chloride in a mixed solvent of 20 mL of octylamine and 15 mL of tri-n-octylphosphine. Under the condition of inert gas, stir and heat until it becomes clear. Then transfer it into an autoclave, and introduce 0.30 mL of tetrabutylammonium borohydride. React under solvothermal reaction conditions of 130 - 140 °C for 5 h under an inert atmosphere, and sub-nanometer size gallium oxide nanowires can be obtained. The sub-nanometer size gallium oxide nanowires obtained in this example are monoclinic. The diameter of the nanowires is 1.0 ± 0.2 nm, and the length is 200 - 300 nm.

Claims

1. A preparation method of sub-nanometer-sized gallium oxide nanowires, characterized in that, The process is as follows: (1) Dissolve 0.1 to 3.0 mmol of inorganic gallium salt in a mixed solvent of 5.0 to 20 mL of organic amine and 5.0 to 20 mL of organic phosphine. Under an inert gas condition, stir and heat to clarity. The inorganic gallium salt is selected from one or more of gallium acetylacetonate, gallium chloride, gallium nitrate, and gallium sulfate. The organic amine is selected from one or more of hexylamine, octylamine, dodecylamine, hexadecylamine, and oleylamine. The organic phosphine is tri-n-octylphosphine, tri-n-butylphosphine, and / or tri-n-octylphosphine oxide. (2) Then add 0.05 to 0.3 mL of an activating reagent to the mixed solvent and react under an inert atmosphere and solvothermal reaction conditions to obtain sub-nanometer-sized gallium oxide nanowires. The activating reagent is sodium borohydride, lithium triethylborohydride, and / or tetrabutylammonium borohydride. React under solvothermal reaction conditions at 80 to 200 °C for 0.5 to 10 h. The diameter of the obtained sub-nanometer-sized gallium oxide nanowires is 1.0 ± 0.2 nm.

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