CN111905750B - Gallium oxide ultrathin sheet, preparation method and application thereof - Google Patents
Gallium oxide ultrathin sheet, preparation method and application thereof Download PDFInfo
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- CN111905750B CN111905750B CN201910388370.XA CN201910388370A CN111905750B CN 111905750 B CN111905750 B CN 111905750B CN 201910388370 A CN201910388370 A CN 201910388370A CN 111905750 B CN111905750 B CN 111905750B
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- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 92
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title description 3
- 229920003023 plastic Polymers 0.000 claims abstract description 46
- 239000004033 plastic Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000004698 Polyethylene Substances 0.000 claims description 26
- 229920000573 polyethylene Polymers 0.000 claims description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical group [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229920000768 polyamine Polymers 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 150000002258 gallium Chemical class 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229940044658 gallium nitrate Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 abstract description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000000089 atomic force micrograph Methods 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 239000012265 solid product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical class [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000003636 chemical group Chemical group 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
-
- 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
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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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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Abstract
The invention provides a gallium oxide ultrathin slice, which is characterized in that the thickness of the gallium oxide ultrathin slice is 0.8-1.2nm, the gallium oxide is gamma-gallium oxide, and the gallium oxide is optionally doped by cobalt with a doping ratio of 0.1-3.0 mol%. The invention also provides a method for preparing the gallium oxide ultrathin slice and a method for converting a plastic product into a gaseous carbon-oxygen compound by utilizing the gallium oxide ultrathin slice through photocatalysis.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a gallium oxide ultrathin slice, a method for preparing the gallium oxide ultrathin slice and a method for converting a plastic product into a gaseous carbon-oxygen compound by photocatalysis by using the gallium oxide ultrathin slice.
Background
Due to the advantages of convenient use, low cost and the like, plastic products play an increasingly important role in the life of people. However, since plastic products are difficult to degrade under natural conditions and difficult to sort and recycle, a large amount of waste plastic products have caused serious environmental problems. Solar energy is a well-known clean and inexhaustible energy source, if we can find a proper catalyst, the plastic products can be efficiently degraded under illumination, and the catalyst is converted into gaseous carbon oxides, so that not only can white pollution be solved, the living environment of people can be improved, but also the dependence of people on fossil raw materials can be reduced, and the solar energy has important significance.
Reports show that gallium oxide has good performance in the aspect of water photolysis, and is a stable and efficient photocatalyst.
In addition, element doping is an important means for improving the performance of the material, and by introducing trace other elements, the optical properties such as light absorption, energy band structure and the like of the raw material can be adjusted, and the introduced elements can also be used as active centers of catalytic reaction, so that the photocatalytic activity of the material is greatly improved.
Therefore, it is necessary to develop a new catalyst capable of efficiently photocatalytic degradation of plastics to produce gaseous hydrocarbons.
Disclosure of Invention
The invention aims to: gallium oxide ultrathin sheets, methods of making, and uses thereof have been developed.
The purpose of the invention is realized by the following technical scheme.
The invention provides a gallium oxide ultrathin slice which is characterized in that the thickness of the gallium oxide ultrathin slice is 0.8-1.2nm, the gallium oxide is gamma-gallium oxide, and the gallium oxide is optionally doped by cobalt with a doping ratio of 0.1-3.0 mol%. Wherein the gallium oxide ultrathin flakes correspond to ultrathin flakes of 2-3 unit cell thicknesses.
Preferably, the gallium oxide ultrathin flakes have a thickness of 1.04-1.06nm, corresponding to an ultrathin flake of 2.5 unit cell thickness.
The invention also provides a method for preparing the gallium oxide ultrathin slice, which comprises the following steps:
dissolving gallium salt and optional cobalt salt in water and stirring;
adding a polyethylene polyamine compound, and stirring again, wherein the number of nitrogen atoms in the polyethylene polyamine compound is 3 to 4;
heating the obtained mixed solution in a sealed reactor for reaction;
cooling the reaction mixture and separating to obtain a solid;
the solid is washed and dried to obtain gallium oxide ultrathin flakes optionally doped with cobalt.
In some embodiments, the gallium salt is gallium nitrate and the cobalt salt is cobalt nitrate.
In some embodiments, the cobalt salt is present in an amount of 0-0.3mmol, the water is present in an amount of 0.1-8mL, and the polyethylene polyamine compound is present in an amount of 10-30mL, relative to 1mmol of the gallium salt.
In some embodiments, the heating reaction is at a reaction temperature of 150 to 180 ℃ and for a reaction time of 24 to 60 hours.
In some embodiments, the separating step is performed by centrifugation.
In some embodiments, the washing step comprises washing the solid multiple times with water and ethanol.
The invention also provides a method for converting plastic products into gaseous carbon-oxygen compounds by photocatalysis, wherein the gallium oxide ultrathin slice is used as a catalyst.
In some embodiments, the method is performed at ambient temperature, pressure, and air atmosphere.
In some embodiments, the plastic article comprises a Polyethylene (PE) plastic article, a polypropylene (PP) plastic article, and a polyethylene terephthalate (PET) plastic article.
The inventor finds that the gallium oxide ultrathin slice has strong photocatalysis capability. The invention also provides a method for simply preparing the gallium oxide ultrathin slice. On the basis, the invention realizes the preparation of gaseous carbon oxygen compound by efficiently degrading plastics through photocatalysis by utilizing the gallium oxide ultrathin sheet in a water system at normal temperature and normal pressure. The method for preparing the gaseous carbon-oxygen compound by photocatalytic conversion of the plastic has high efficiency, is simple and practical, and is convenient for large-scale application
Drawings
FIG. 1 is XRD diffraction patterns of cobalt-doped gallium oxide ultrathin flakes (a) prepared in example 2 and undoped gallium oxide ultrathin flakes (b) prepared in example 1.
FIG. 2 is an XPS spectrum of Co 2p orbitals of cobalt-doped ultrathin flakes of gallium oxide prepared in example 2.
FIG. 3 is a Transmission Electron Micrograph (TEM) of cobalt-doped gallium oxide ultrathin flakes prepared in example 2.
FIG. 4 is a Transmission Electron Micrograph (TEM) of an undoped gallium oxide ultrathin sheet prepared in example 1.
FIG. 5 is an atomic force microscope image (AFM) of cobalt-doped gallium oxide ultrathin flakes prepared in example 2.
FIG. 6 is an atomic force microscope image (AFM) of an undoped gallium oxide ultrathin sheet prepared in example 1.
FIG. 7 is a photograph of (A) a PE plastic bag and (B) a powder obtained by crushing the PE plastic bag.
FIG. 8 is a photograph of powders obtained by (A) and (B) crushing of a PP plastic packing box.
FIG. 9 is a photograph of (A) a PET bottle and (B) a powder obtained by pulverizing the PET bottle.
FIG. 10 is a graph showing the generation rates of carbon monoxide and carbon dioxide by photocatalytic conversion of PE plastic bags using cobalt-doped gallium oxide ultrathin sheets prepared in example 2 and undoped gallium oxide ultrathin sheets prepared in example 1.
FIG. 11 is a graph of the production rates of carbon monoxide and carbon dioxide using the cobalt-doped gallium oxide ultrathin sheets prepared in example 2 and the undoped gallium oxide ultrathin sheets prepared in example 1 to photocatalytically convert PP plastic packing boxes.
FIG. 12 is a graph showing the rate of formation of carbon monoxide and carbon dioxide by photocatalytic conversion of PET plastic bottles using cobalt-doped gallium oxide ultrathin sheets prepared in example 2 and undoped gallium oxide ultrathin sheets prepared in example 1.
Detailed Description
Example 1
256mg of gallium nitrate (Aladdin reagent Co., ltd.) was dissolved in 5mL of water (redistilled water), and vigorously stirred for 10min. Then, 30mL of triethylene tetramine (national chemical group, chemical Co., ltd.) was added thereto, and the mixture was vigorously stirred for 30min. Then, the resulting mixture was transferred to a 40mL autoclave and sealed, and placed in an oven (Shanghai sperm macro laboratory Equipment Co., ltd., XMTD-8222) to be heated to 160 ℃ for reaction for 48 hours. Naturally cooling to room temperature after the reaction is finished, centrifugally separating in a high-speed centrifuge (HC-3518 of China scientific instruments Co., ltd., anhui Zhongke) at 14000rpm to obtain a solid product, washing with water and ethanol (chemical reagents Co., ltd., national drug group) for several times, and finally drying in a vacuum drying oven at 60 ℃ for 12h to obtain the powdery undoped gallium oxide ultrathin sheet.
The compounds prepared in this example were characterized using an XRD instrument (Philips X' Pert Pro Super diffractometer), a transmission electron microscope (JEOLJEM-ARM 200F) and an atomic force microscope (Veeco DI Nano-scope Multimode V system), and the results are shown in FIGS. 1, 4 and 6. FIG. 1 shows the XRD diffraction pattern of an undoped gallium oxide ultrathin flake (b) prepared in example 1; FIG. 4 shows a Transmission Electron Micrograph (TEM) of an undoped gallium oxide ultrathin sheet prepared in example 1; FIG. 6 shows an atomic force microscope image (AFM) of an undoped gallium oxide ultrathin sheet prepared in example 1. As can be seen from FIG. 6, the thickness of the prepared undoped gallium oxide ultrathin sheet is 1.05-1.06nm, corresponding to an ultrathin sheet of 2.5 unit cell thickness.
Example 2
256mg of gallium nitrate (Allantin reagent Co., ltd.) and 29mg of cobalt nitrate (Allantin reagent Co., ltd.) were dissolved in 5mL of water (redistilled water), and vigorously stirred for 10min. Then, 30mL of triethylenetetramine (national chemical group chemical Co., ltd.) was added thereto, and the mixture was vigorously stirred for 30min. Then, the resulting mixture was transferred to a 40mL autoclave and sealed, and placed in an oven (Shanghai sperm macro laboratory Equipment Co., ltd., XMTD-8222) to be heated to 160 ℃ for reaction for 48 hours. After the reaction is finished, the mixture is naturally cooled to room temperature, and is centrifugally separated in a high-speed centrifuge (HC-3518 of Ching scientific instruments Co., ltd., anhui Zhongke) at the rotating speed of 14000rpm to obtain a solid product, the solid product is washed for a plurality of times by water and ethanol (chemical reagents Co., ltd., national drug group), and finally the solid product is dried in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the powdery cobalt-doped gallium oxide ultrathin sheet.
The compound prepared in this example was characterized by using an XRD instrument (Philips X' Pert Pro Super differential meter), X-ray photoelectron spectroscopy (ESCLAB MK II), transmission electron microscopy (JEOL JEM-ARM 200F) and atomic force microscopy (Veeco DI Nano-scope Multimode V system), and the results are shown in FIGS. 1 to 3 and 5. FIG. 1 shows the XRD diffraction pattern of cobalt-doped gallium oxide ultrathin flakes (a) prepared in example 2; FIG. 2 shows an X-ray photoelectron spectrum of Co 2p orbitals of cobalt-doped gallium oxide ultrathin flakes prepared in example 2; FIG. 3 shows a transmission electron micrograph of cobalt-doped gallium oxide ultrathin sheets prepared in example 2; fig. 5 shows an atomic force microscope image (AFM) of the cobalt-doped gallium oxide ultrathin sheet prepared in example 2. As can be seen from FIG. 5, the prepared cobalt-doped gallium oxide ultrathin slices have a thickness of 1.04-1.06nm, corresponding to an ultrathin slice with a thickness of 2.5 unit cells.
Comparative example 1
256mg of gallium nitrate (Allantin reagent Co., ltd.) and 29mg of cobalt nitrate (Allantin reagent Co., ltd.) were dissolved in 5mL of water (redistilled water), and vigorously stirred for 10min. Then, 30mL of triethylenetetramine (national chemical group chemical Co., ltd.) was added thereto, and the mixture was vigorously stirred for 30min. Then, the resulting mixture was transferred to a 40mL autoclave and sealed, and placed in an oven (Shanghai Jing Macro laboratory facilities, inc. XMTD-8222) to be heated to 80 ℃ for reaction for 48 hours. After the reaction, the reaction mixture was naturally cooled to room temperature, centrifuged in a high speed centrifuge (HC-3518, zhonghui science instruments Co., ltd., anhui Zhongke) at 14000rpm to obtain a solid product, washed several times with water and ethanol (Chemicals, inc., national medicine group), and finally dried in a vacuum drying oven at 60 ℃ for 12 hours. The resulting product was not ultrathin gallium oxide characterized in detail.
Comparative example 2
256mg of gallium nitrate (Allantin reagent Co., ltd.) and 29mg of cobalt nitrate (Allantin reagent Co., ltd.) were dissolved in 5mL of water (redistilled water), and vigorously stirred for 10min. Then, 30mL of ethylenediamine (national chemical group, chemical Co., ltd.) was added thereto, and the mixture was vigorously stirred for 30min. Then, the resulting mixture was transferred to a 40mL autoclave and sealed, and placed in an oven (Shanghai sperm macro laboratory Equipment Co., ltd., XMTD-8222) to be heated to 160 ℃ for reaction for 48 hours. After the reaction, the reaction mixture was naturally cooled to room temperature, and centrifuged in a high-speed centrifuge (HC-3518, zhongzhongjia scientific instruments Co., ltd.) at 14000rpm to obtain a solid product, which was washed several times with water and ethanol (chemical reagents Co., ltd., national drug group) and finally dried in a vacuum oven at 60 ℃ for 12 hours. The resulting product was not ultrathin gallium oxide characterized in detail.
Application example 1: the obtained gallium oxide ultrathin sheet is subjected to photocatalytic conversion to generate carbon monoxide and carbon dioxide by commercial PE plastic bags
50mg of the undoped gallium oxide ultrathin sheet of example 1 or the cobalt-doped gallium oxide ultrathin sheet of example 2 and 100mg of powder (fig. 7) obtained by pulverizing a commercial PE plastic bag were dispersed in 100mL of water, and the amount of generated carbon monoxide and carbon dioxide was measured by continuous light irradiation at normal temperature, normal pressure and air atmosphere with 300W xenon lamp (kindey, china, and education, science and technology ltd) as a light energy source for the reaction.
FIG. 10 is a graph showing the rate of formation of carbon monoxide and carbon dioxide in photocatalytic conversion PE plastic bag applications for an undoped gallium oxide ultrathin sheet prepared according to example 1 of the present invention and a cobalt-doped gallium oxide ultrathin sheet prepared according to example 2 of the present invention. As can be seen from fig. 10, both the undoped gallium oxide ultrathin sheet and the cobalt-doped gallium oxide ultrathin sheet obtained by the present invention can realize photocatalytic conversion of a PE plastic bag to gaseous carbon-oxygen compounds at normal temperature and normal pressure by using water as a solvent; compared with the undoped gallium oxide ultrathin slice, the cobalt-doped gallium oxide ultrathin slice obtained by the invention has the rate of generating carbon monoxide and carbon dioxide by catalytically converting PE plastic bags under illumination by about 1.9 and 1.6 times respectively.
Application example 2: the obtained gallium oxide ultrathin sheet is subjected to photocatalytic conversion to generate carbon monoxide and carbon dioxide in a PP plastic packing box
50mg of the undoped gallium oxide ultrathin sheet of example 1 or the cobalt-doped gallium oxide ultrathin sheet of example 2 and 100mg of powder (fig. 8) obtained by pulverizing a commercial PP plastic packing box were dispersed in 100mL of water, and the amount of generated carbon monoxide and carbon dioxide was measured by continuous light irradiation at normal temperature and pressure in an air atmosphere with a 300W xenon lamp (kindek, inc., science and technology ltd.) as a light energy source for the reaction, with the use of light energy from a 300W xenon lamp (beijing, zhongjinyuan scientific co.).
FIG. 11 is a graph showing the rate of formation of carbon monoxide and carbon dioxide in photocatalytic conversion PP plastic carton applications for an undoped gallium oxide ultrathin sheet prepared according to example 1 of the present invention and a cobalt-doped gallium oxide ultrathin sheet prepared according to example 2 of the present invention. As can be seen from fig. 11, both the undoped gallium oxide ultrathin sheet and the cobalt-doped gallium oxide ultrathin sheet obtained by the present invention can realize photocatalytic conversion of a PP plastic packaging box to gaseous carbon-oxygen compounds at normal temperature and normal pressure by using water as a solvent; compared with the undoped gallium oxide ultrathin slice, the cobalt-doped gallium oxide ultrathin slice obtained by the invention has the speed of catalyzing and converting a PP plastic packing box into carbon monoxide and carbon dioxide under illumination by about 1.9 and 1.5 times respectively.
Application example 3: the obtained gallium oxide ultrathin sheet is subjected to photocatalytic conversion to generate carbon monoxide and carbon dioxide by commercial PET plastic bottles
50mg of the undoped gallium oxide ultrathin sheet of example 1 or the cobalt-doped gallium oxide ultrathin sheet of example 2 and 100mg of powder (fig. 9) obtained by pulverizing a commercial PET plastic bottle were dispersed in 100mL of water, and the amount of carbon monoxide and carbon dioxide generated was measured by continuous irradiation with light at normal temperature, normal pressure and air atmosphere with a 300W xenon lamp (the kindey, china, and the science and technology ltd) as a light energy source for the reaction.
FIG. 12 is a graph showing the rate of formation of carbon monoxide and carbon dioxide in a photocatalytic conversion commercial PET plastic bottle application for an undoped gallium oxide ultrathin sheet prepared according to inventive example 1 and a cobalt-doped gallium oxide ultrathin sheet prepared according to inventive example 2. As can be seen from fig. 12, both the undoped gallium oxide ultrathin sheet and the cobalt-doped gallium oxide ultrathin sheet obtained by the present invention can realize photocatalytic conversion of commercial PET plastic bottles to gaseous carbon-oxygen compounds at normal temperature and normal pressure by using water as a solvent; compared with the undoped gallium oxide ultrathin slice, the cobalt-doped gallium oxide ultrathin slice obtained by the invention has the rate of catalytically converting a commercial PET plastic bottle into carbon monoxide and carbon dioxide under illumination by about 1.6 and 1.6 times respectively.
Comparative example 3: undoped gallium oxide ultrathin sheet of example 1 was catalytically converted to commercial PE plastic bag without addition of light
After 50mg of the undoped gallium oxide ultra-thin flake obtained by example 1 and 100mg of powder obtained by pulverizing a commercial PE plastic bag (fig. 7) were dispersed in 100mL of water and continuously stirred for 24 hours at normal temperature, pressure and air atmosphere, no product was detected.
Comparative example 4: cobalt-doped gallium oxide ultrathin flakes of example 2 were catalytically converted into commercial PE plastic bags without the addition of light
After 50mg of cobalt-doped gallium oxide ultra-thin flake obtained by example 2 and 100mg of powder obtained by pulverizing a commercial PE plastic bag (fig. 7) were dispersed in 100mL of water and continuously stirred for 24 hours at normal temperature and pressure in air atmosphere, no product was detected.
Comparative example 5: photocatalytic conversion of commercial PE plastic bags without catalyst
100mg of powder (FIG. 7) obtained by pulverizing a commercial PE plastic bag was dispersed in 100mL of water, and a 300W xenon lamp (Miao jin Yuan science and technology Co., ltd., beijing) was used as a light energy source for the reaction, and the light irradiation was continued at normal temperature and pressure in the air atmosphere, and no product was detected after 24 hours of the reaction.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (8)
1. A gallium oxide ultrathin flake having a thickness of 0.8 to 1.2nm, said gallium oxide being γ -gallium oxide, optionally doped with cobalt at a doping ratio of 0.1 mol% to 3.0 mol%, wherein said gallium oxide ultrathin flake is prepared by a process comprising the steps of:
dissolving gallium salt and optional cobalt salt in water and stirring;
adding a polyethylene polyamine compound, and stirring again, wherein the number of nitrogen atoms in the polyethylene polyamine compound is 3 to 4;
heating the obtained mixed solution in a sealed reactor for reaction, wherein the reaction temperature of the heating reaction is 150-180 ℃, and the reaction time is 24-60 hours;
cooling the reaction mixture and separating to obtain a solid;
washing and drying the solid to obtain gallium oxide ultrathin flakes optionally doped with cobalt,
relative to 1mmol of gallium salt, the dosage of the cobalt salt is 0-0.3mmol, the dosage of water is 0.1-8mL, and the dosage of the polyethylene polyamine compound is 10-30mL.
2. A method of making the gallium oxide ultrathin sheet of claim 1, the method comprising:
dissolving a gallium salt and optionally a cobalt salt in water and stirring;
adding a polyethylene polyamine compound, and stirring again, wherein the number of nitrogen atoms in the polyethylene polyamine compound is 3 to 4;
heating the obtained mixed solution in a sealed reactor for reaction, wherein the reaction temperature of the heating reaction is 150-180 ℃, and the reaction time is 24-60 hours;
cooling the reaction mixture and separating to obtain a solid;
washing and drying the solid to obtain gallium oxide ultrathin slices optionally doped with cobalt,
relative to 1mmol of gallium salt, the dosage of the cobalt salt is 0-0.3mmol, the dosage of water is 0.1-8mL, and the dosage of the polyethylene polyamine compound is 10-30mL.
3. The method of claim 2, wherein the gallium salt is gallium nitrate and the cobalt salt is cobalt nitrate.
4. The method of claim 2, wherein the separating step is performed by centrifugation.
5. The method of claim 2, wherein the washing step comprises washing the solid multiple times with water and ethanol.
6. A method for converting plastic articles into gaseous carbon oxides by photocatalysis, wherein the gallium oxide ultrathin flakes of claim 1 are used as a catalyst.
7. The method of claim 6, wherein the method is performed at normal temperature, normal pressure, and air atmosphere.
8. The method of claim 6, wherein the plastic article comprises PE plastic, PP plastic, and PET plastic.
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