Aluminum nanosheet, its preparing method and use thereof
20180169753 ยท 2018-06-21
Assignee
Inventors
Cpc classification
B22F2202/17
PERFORMING OPERATIONS; TRANSPORTING
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
Y10S977/81
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
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
B22F9/24
PERFORMING OPERATIONS; TRANSPORTING
B22F2998/10
PERFORMING OPERATIONS; TRANSPORTING
Y10S977/755
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
B22F2998/10
PERFORMING OPERATIONS; TRANSPORTING
B22F9/24
PERFORMING OPERATIONS; TRANSPORTING
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
Y10S977/95
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
B22F1/142
PERFORMING OPERATIONS; TRANSPORTING
Y10S977/896
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
B22F1/056
PERFORMING OPERATIONS; TRANSPORTING
B22F1/142
PERFORMING OPERATIONS; TRANSPORTING
B22F2202/17
PERFORMING OPERATIONS; TRANSPORTING
International classification
B22F1/00
PERFORMING OPERATIONS; TRANSPORTING
B22F9/24
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention provides an aluminum nanosheet, having an equivalent diameter of 50 to 1000 nm, and a thickness of 1.5 to 50 nm. The invention further provides a method for preparing the aluminum nanosheet and the use thereof as a two-photon light emitting material or a Raman enhanced material.
Claims
1. An aluminum nanosheet having an equivalent diameter within a range from 50 to 1000 nm, and a thickness within a range from 1.5 to 50 nm.
2. A method for preparing an aluminum nanosheet comprising: preparing a first reaction solution by adding an aluminum source and an organic ligand to a first organic solvent; preparing a second reaction solution by adding lithium aluminum hydride to a second organic solvent; performing a reductive reaction by adding the second reaction solution to the first reaction solution, wherein a resultant mixture reacts at a temperature within a range from 100 C. to 165 C. for 1 to 72 hours, to produce an aluminum nanosheet suspension; performing a solid-liquid separation on the aluminum nanosheet suspension; wherein a produced solid is the aluminum nanosheet; and the aluminum nanosheet having an equivalent diameter within a range from 50 to 1000 nm, and a thickness within a range from 1.5 to 50 nm.
3. The method according to claim 2, wherein the solid-liquid separation step comprises: performing a concentration centrifugation; performing an ultrasonic washing; and performing a vacuum drying; wherein washing liquid used in the ultrasonic washing is selected from the group consisting of acetone, methanol and ether or a mixture thereof.
4. The method according to claim 2 wherein the aluminum source is selected from the group consisting of aluminum chloride, aluminum acetylacetonate, and aluminum acetate or a mixture thereof; the organic ligand is selected from the group consisting of polyethylene glycol, polyvinylpyrrolidone, polymethylmethacrylate, polyethylene glycol dimethyl ether and oleyl amine; the first and second organic solvents, independently of each other, are one or more selected from the group consisting of toluene, mesitylene and butyl ether.
5. The method according to claim 2 wherein, the amount of the organic ligand is selected so that a molar ratio of the organic ligand to the aluminum nanosheet is 1:(0.01-5).
6. The method according to claim 4 wherein when aluminum chloride is used as the aluminum source, a concentration of aluminum chloride is within a range from 0.01 to 1 mol/L, and a molar ratio of the aluminum chloride to the lithium aluminum hydride is 1:(0.1-4); when aluminum acetylacetonate or aluminum acetate is used as the aluminum source, a concentration of aluminum acetylacetonate or aluminum acetate is within a range from 0.01 to 1 mol/L, and a molar ratio of the aluminum acetylacetonate or the aluminum acetate to the lithium aluminum hydride is 1:(0.05-3).
7. The method according to claim 2 wherein the reductive reaction is performed under an oxygen-containing atmosphere with an autogenous pressure in a closed reaction vessel, wherein the oxygen-containing atmosphere has an oxygen concentration within a range from 15 vol % to 50 vol %; alternatively, the reductive reaction is performed under a normal pressure in an opening reaction vessel.
8. The method according claim 2 wherein the second reaction solution is added into the first reaction solution completely or partially.
9. The method according to claim 2 wherein the thickness of the aluminum nanosheet is reduced by selecting the organic ligand having a relatively higher mass proportion of nitrogen or oxygen element; alternatively, when the same organic ligand is used, the thickness of the aluminum nanosheet is reduced by reducing the molar ratio of the organic ligand to the aluminum source.
10. The aluminum nanosheet according to claim 1 is used as a two-photon light emitting material or a Raman enhanced material.
11. The aluminum nanosheet according to claim 1 is used for increasing a light emitting intensity of a two-proton light emitting material; or, for expanding an intrinsic light emitting region from an ultraviolet region to a near infrared region by reducing the thickness of the aluminum nanosheet.
12. The method according claim 3 wherein the second reaction solution is added into the first reaction solution completely or partially.
13. The method according claim 4 wherein the second reaction solution is added into the first reaction solution completely or partially.
14. The method according claim 5 wherein the second reaction solution is added into the first reaction solution completely or partially.
15. The method according claim 6 wherein the second reaction solution is added into the first reaction solution completely or partially.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
[0043] The following text further describes the invention by combining the drawings and the examples. However, it should be understood that the following specific examples are only used for illustrating the invention, but not limiting the invention in any form.
Embodiment 1
[0044] 0.665 g of aluminum chloride (a metal salt), and 0.27 g of polyvinylpyrrolidone (PVP) were dissolved in 10 ml of mesitylene, and the resultant mixture was stirred at 80 C. for 5 minutes to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 0.57 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene to form a solution B. The solution B was added to the above flask in once, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 20 vol % oxygen till saturation and the air above the liquid surface is vented. The flask was placed in an oil bath in which the reaction was carried on for 4 hours at 140 C., and then the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 minutes with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of acetone, and after the dispersed suspension was ultrasonically treated for 5 minutes, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
Embodiment 2
[0045] 1.621 g of aluminum chloride (a metal salt), and 0.5 g of polyethylene glycol dimethyl ether (NHD) were dissolved in 10 ml of mesitylene, and the resultant mixture was stirred for at 80 C. 5 minutes to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 1.14 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene to form a solution B. The solution B was added to the above flask in once, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 40 vol % oxygen till saturation and the air above the liquid surface is vented. The flask was placed in an oil bath in which the reaction was carried on for 10 hours at 140 C., and then the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 min with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of ether, and after the dispersed suspension was ultrasonically treated for 5 minutes it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
Embodiment 3
[0046] 0.33 g of aluminum chloride (a metal salt), and 0.01 g of polyvinylpyrrolidone (PVP) were dissolved in 10 ml of mesitylene, and the resultant mixture was stirred at 80 C. for 5 minutes to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 0.057 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene to form a solution B. The solution B was added to the above flask in once, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 30 vol % oxygen till saturation and the air above the liquid surface is vented. The flask was placed in an oil bath in which the reaction was carried on for 3 hours at 165 C., and then the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 minutes with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of acetone, and after the dispersed suspension was ultrasonically treated for 5 min, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
[0047] Table 1 shows the comparisons between the aluminum nanosheet as prepared in Example 3 of the invention and the pure polyvinylpyrrolidone (PVP). As seen from the table, the aluminum nanomaterial as encapsulated with polyvinylpyrrolidone can exhibit the variation in the combination energy of N1s and O1s as compared to pure polyvinylpyrrolidone. Furthermore, it can be seen that aluminum is directly bonded to nitrogen and oxygen atoms, and just due to such a direct bonding, organic ligands containing nitrogen or oxygen atoms can produce controls to the morphology of the sheet structure and oxidization of the aluminum nanosheet.
TABLE-US-00001 TABLE 1 Peak Position Sample Element PVP PVP@Al N 399.4 399.7 O 530.95 531.61
Embodiment 4
[0048] 0.066 g of aluminum chloride (a metal salt), and 0.25 g of polymethyl methacrylate (PMMA) were dissolved in 10 ml of toluene, and the resultant mixture was stirred at 80 C. for 5 minutes to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 0.076 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of toluene to form a solution B. The solution B was added to the above flask in once, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 15 vol % oxygen till saturation and the air above the liquid surface is vented. The flask was placed in an oil bath in which the reaction carried on for 48 hours at 110 C., and then the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 min with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of icy methanol, and after the dispersed suspension was ultrasonically treated for 5 minutes, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
Embodiment 5
[0049] 0.162 g of aluminum acetylacetonate (a metal salt) were dissolved in 10 ml of oleyl amine, and the resultant mixture was stirred for 5 min at room temperature to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 0.057 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene to form a solution B. The solution B was averagely divided into 10 parts in constant volume. One part of the solution B was added to the above flask in once, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 20 vol % oxygen till saturation and the air above the liquid surface is vented. The flask was placed in an oil bath in which the reaction was carried on for 10 hours at 165 C., and as the reaction time went on, one part of the solution B was added to the flask every hour. After the reaction was completed, the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 minutes with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of icy methanol, and after the dispersed suspension was ultrasonically treated for 5 minutes, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
Embodiment 6
[0050] A mixture of 0.0495 g of aluminum chloride and 0.0405 g of aluminum acetylacetonate (a metal salt) and 0.01 g of polyethylene glycol (PEG) were dissolved in 10 ml of mesitylene, and the resultant mixture was stirred at 80 C. for 5 min to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 0.057 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene to form a solution B. The solution B was added to the above flask in once, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 45 vol % oxygen till saturation and the air above the liquid surface is vented. The flask was placed in an oil bath in which the reaction was carried on for 48 hours at 120 C., and then the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 min with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of acetone, and after the dispersed suspension was ultrasonically treated for 5 minutes, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
Embodiment 7
[0051] 0.510 g of aluminum acetate (a metal salt), and 0.54 g of polyvinylpyrrolidone (PVP) were dissolved in 10 ml of mesitylene, and the resultant mixture was stirred at 80 C. for 5 minute to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 0.038 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene to form a solution B. The solution B was added to the above flask in once, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 30 vol % oxygen till saturation and the air above the liquid surface is vented. The flask was placed in an oil bath in which the reaction carried on for 8 hours at 120 C., and then the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 min with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of acetone, and after the dispersed suspension was ultrasonically treated for 5 minute, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
Embodiment 8
[0052] 0.26 g of aluminum acetate (a metal salt), and 0.01 g of polyethylene glycol (PEG) were dissolved in 10 ml of mesitylene, and the resultant mixture was stirred at 80 C. for 5 minutes to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 0.057 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene to form a solution B. The solution B was added to the above flask in once, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 20 vol % oxygen till saturation and the air above the liquid surface is vented. The flask was placed in an oil bath in which the reaction was carried on for 10 hours at 120 C., and then the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 min with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of acetone, and after the dispersed suspension was ultrasonically treated for 5 minute, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
Embodiment 9
[0053] A mixture of 0.052 g of aluminum chloride and 0.032 g of aluminum acetylacetonate (a metal salt), and 0.01 g of polyvinylpyrrolidone (PVP) were dissolved in 10 ml of mesitylene, and the resultant mixture was stirred at 80 C. for 5 min to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was placed in a reactor. Thereafter, 0.057 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene to form a solution B. The solution B was added in once to the above reactor containing the solution A, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 50 vol % oxygen till saturation and the air above the liquid surface is vented. The reactor was closed and placed in a thermostat in which the reaction was carried on for 10 hours at 165 C., and then the reactor was taken out of the thermostat and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 min with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of acetone, and after the dispersed suspension was ultrasonically treated for 5 minutes, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
Embodiment 10
[0054] 0.665 g of aluminum chloride (a metal salt) was dissolved in 10 ml of mesitylene, and the resultant mixture was stirred at 80 C. for 5 min to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 0.57 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene to form a solution B. The solution B was added in once to the above flask containing the solution A, and with violent stirring, the two solutions were homogenously mixed. The mixed solution was bubbled with nitrogen/oxygen mixed gas containing 15 vol % oxygen till saturation and the air above the liquid surface is vented. The flask was placed in oil bath in which the reaction was carried on for 4 hours at 140 C., and then the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 min with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of acetone, and after the dispersed suspension was ultrasonically treated for 5 minutes, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
Embodiment 11
[0055] Argon was continuously bubbled into 20 ml of mesitylene for 20 minutes to sufficiently remove the dissolved oxygen in the solvent as much as possible. The solvent from which the dissolved oxygen has been removed is then placed in an oxygen-free glove box. The following steps were carried out in the glove box. 0.665 g of aluminum chloride (a metal salt), and 0.27 g of polyvinylpyrrolidone (PVP) were dissolved in 10 ml of mesitylene from which the dissolved oxygen has been removed, and the resultant mixture was stirred at 80 C. for 5 minutes to fully dissolve the above materials therein, thereby to form a homogenous solution A. The resultant solution was transferred into a 25 ml flask. Thereafter, 0.057 g of lithium aluminum hydride (a reductive agent) was dissolved in 10 ml of mesitylene from which the dissolved oxygen has been removed to form a solution B. The solution B was added to the above flask, and with violent stirring, the two solutions were homogenously mixed. The flask was placed in an oil bath in which the reaction was carried on for 4 hours at 140 C., and then the flask was taken out of the oil bath and naturally cooled in air. The cooled solution was poured into a centrifugal tube to be centrifugation concentrated for 20 min with the rotary speed of 5000 rpm, and the resultant supernatant fluid was removed. Then, the concentrated suspension was dispersed with 15 ml of acetone, and after the dispersed suspension was ultrasonically treated for 5 minute, it was centrifugation washed at the rotary speed of 8000 rpm. The above operations were repeated three times. The resultant product was dried under vacuum, and it was stored under oxygen isolation.
[0056] The experimental results as shown by the drawings are sufficient to prove that the material as synthesized in the invention is a metal aluminum nanosheet having a specified morphology and a certain dispersing ability. The invention is an important progress in the field of the preparation of aluminum metal materials.