CN111215044A - Ga based on flexible substrate2O3Nano-column photocatalytic material and preparation method thereof - Google Patents
Ga based on flexible substrate2O3Nano-column photocatalytic material and preparation method thereof 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/48—Coating with two or more coatings having different compositions
- C03C25/52—Coatings containing inorganic materials only
Abstract
The invention relates to Ga based on a flexible substrate2O3The nano-column photocatalytic material comprises a flexible substrate layer and SnO positioned on the flexible substrate layer2A seed layer located on the SnO2Ga on seed layer2O3Nanopillar array, the Ga2O3The nanopillar array is composed of a plurality of Ga2O3The nano-columns are arranged in a spaced array, and the Ga2O3The cross section of the nano-column is quadrilateral. The invention synthesizes Ga on a flexible substrate in situ2O3The nano-column has the advantages of firm combination, good stability, good photocatalytic performance, large specific surface area, easy recovery and separation, and suitability for industrial production.
Description
Technical Field
The invention relates to the field of gallium oxide nanorod photocatalysis, in particular to Ga based on a flexible substrate2O3Nano-pillar array and preparation method thereof
Background
With the continuous development of human science and technology, the problems of energy crisis and environmental pollution gradually become important factors restricting the economic development of all countries around the world. The photocatalysis process can utilize light energy to decompose waste gas and industrial wastewater into inorganic micromolecular substances such as water, carbon dioxide and the like, or obtain clean energy by photolysis of water to produce hydrogen, so the photocatalysis process has wide application prospect in the fields of environment and energy.
Various photocatalysts have been developed, among which Ga2O3As a novel wide-bandgap semiconductor, the semiconductor has a bandgap of 4.8eV, has good chemical stability and thermal stability, and its wide bandgap greatly improves the mobility rate of photo-generated electrons and effectively promotes charge separation. With commercial TiO2Particle phase ratio of Ga2O3Has better photocatalysis performance because it can provide more proper oxidation-reduction potential for photogenerated charge carriers, thereby providing higher driving force for photocatalysis. While Ga2O3Is also an environment-friendly material, has no toxicity, and has certain advantages in the field of photocatalysis.
Reported about Ga2O3As the Ga in the form of nano particles or nano columns synthesized by a hydrothermal method or a solution precipitation method in the photocatalysis research2O3The catalyst and the wastewater form a suspension system, however, the suspension system has the defects of easy coagulation and poisoning of the catalyst, insufficient light receiving and the like due to the subsequent separation and recovery, and the like, so the practical application of the suspension system is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides Ga based on a flexible substrate2O3The nano-column photocatalytic material and the preparation method thereof can effectively solve the problems of difficult recovery of catalyst such as fixation, separation and the like and insufficient absorption of illumination.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: ga based on flexible substrate2O3The nano-pillar photocatalytic material comprises a flexible substrate layer and SnO positioned on the flexible substrate layer2A seed layer located on the SnO2Ga on seed layer2O3Nanopillar array, structureGa as described above2O3The nanopillar array is composed of a plurality of Ga2O3The nano-columns are arranged in a spaced array, and the Ga2O3The cross section of the nano-column is quadrilateral.
Wherein the Ga is2O3The height of the nano column is 1-2 mu m, and the diagonal length of the cross section is 80-500 nm.
Wherein the Ga is2O3the nano-column array is α -Ga2O3nanopillar array, α/β -Ga2O3combined with nano-column array or β -Ga2O3An array of nanopillars.
Preferably, the flexible substrate layer is a flexible glass fiber substrate.
The invention also comprises a second technical scheme, namely the preparation of the Ga based on the flexible substrate2O3A method of nano-pillar photocatalytic material, comprising:
depositing a layer of SnO on a flexible substrate by radio frequency magnetron sputtering under vacuum2Film and annealing to form flexible substrate/SnO2A seed crystal layer;
bonding a Flexible substrate/SnO2A seed layer is arranged on Ga (NO)3)3In the water solution, carrying out hydrothermal reaction to form a GaOOH nano-column array;
calcining for 4 hours at 400 ℃ to obtain α -Ga2O3A nanopillar array;
and subjected to secondary calcination at 700 ℃ to form Ga2O3Nanopillar arrays, i.e. obtaining Ga based on flexible substrates2O3The nano-pillar array is made of a photocatalytic material.
Wherein, the Ga (NO)3)3The concentration of the aqueous solution is 6.7-20mg/mL, the temperature of the hydrothermal reaction is 150 ℃, and the time of the hydrothermal reaction is 8-12 h.
Wherein the specific parameter of the radio frequency magnetron sputtering is that the vacuum degree of a cavity is 5 multiplied by 10-4Pa, working atmosphere Ar and O2Ar and O2The ratio of (1-2) to (1), the working pressure is 0.8Pa, the temperature of the flexible substrate is 550 ℃, the sputtering power is 100W, and the sputtering time is 4 h.
Wherein the annealing temperature is 550 ℃, and the annealing time is 2 h.
Wherein the flexible substrate/SnO2A seed layer is arranged on Ga (NO)3)3In the aqueous solution, the flexible substrate/SnO is2The seed crystal layer is fixed on the glass slide, and the glass slide and the flexible substrate/SnO are fixed on the glass slide2The seed crystal layer leans against the inner wall of the high-pressure reaction kettle, and then hydrothermal reaction is carried out.
Wherein the time of the secondary calcination is 20-120 min.
The flexible glass fiber substrate is subjected to pretreatment, namely ultrasonic cleaning is carried out on the flexible glass fiber substrate for 10min by respectively using acetone, absolute ethyl alcohol and deionized water, and then dry N is used2Air-dried and dried in an oven at 60 ℃ for 12 h.
The invention has the beneficial effects that:
(1) ga of the invention based on Flexible substrate2O3Nanoprost photocatalytic material based on a flexible substrate, Ga2O3The cross section of the nano-column is quadrilateral, the morphology is uniform, and the formed Ga2O3The nano-column photocatalytic material has larger specific surface area, can absorb light more fully, can effectively solve the problem of difficult recovery of catalyst such as fixation, separation and the like, and is suitable for large-scale industrial popularization.
(2) Ga of the invention based on Flexible substrate2O3Nanopillar photocatalytic material, Ga2O3The nano-column array has high specific surface area, uniform appearance and size, and Ga2O3Ga in nanopillar array2O3Nano-pillars spaced apart, Ga2O3With gaps between the nano-pillars, so that the Ga is based on a flexible substrate2O3The surface of the nano-column photocatalytic material is porous and has strong light absorption.
(3) Ga of the invention based on Flexible substrate2O3the nano-column photocatalytic material can be α phase, β phase or alpha/β phase2O3Nanopillar array such that Ga2O3The combined nano-column is beneficial to the separation of photon-generated carriers.
(4) Ga of the invention based on Flexible substrate2O3The nano-column photocatalysis material has the advantages of high strength, acid and alkali resistance, corrosion resistance and the like, and compared with other carriers, the flexible glass fiber substrate is an excellent inorganic nonmetal material, has larger specific surface area, and can load Ga in large area2O3And (4) nano columns.
(5) The preparation method of the invention is to synthesize Ga in situ on the flexible substrate2O3Nanopillar array, flexible substrate-based Ga formed2O3The nano-pillar has stable structure, Ga2O3The nano-column is not easy to fall off, and the preparation method is simple, low in cost, good in repeatability, green and environment-friendly, and easy for industrial production.
(6) The preparation method of the invention can obtain Ga with different phases by secondary calcination and controlling the time of the secondary calcination2O3The nano-column is beneficial to the separation of photon-generated carriers.
Drawings
FIG. 1 shows Ga synthesized by the method of the present invention2O3Flow chart of nano-pillar photocatalytic material.
FIG. 2 α -Ga obtained by the process of the present invention2O3An SEM photograph of the nanopillar array.
FIG. 3 shows α -Ga obtained by the process of the present invention2O3Still another SEM photograph of the nanopillar array.
FIG. 4 shows Ga of different phase structure obtained by the process of the present invention2O3XRD pattern of nanopillar array.
FIG. 5 shows Ga of different phase structure obtained by the method of the present invention2O3Raman map of nanopillar array.
FIG. 6 shows Ga of different phase structure obtained by the method of the present invention2O3The degradation performance of the nano-column photocatalytic material to the RhB aqueous solution under the irradiation of 254nm ultraviolet light is shown.
FIG. 7 shows α/β -Ga obtained by the method of the present invention2O3Phase combination photocatalysisIn the presence of the reagent, the absorption spectrum of the RhB aqueous solution changes within 60min of ultraviolet irradiation.
Detailed Description
The invention is further explained below with reference to examples and figures.
The invention provides a Ga based on a flexible substrate2O3The nano-pillar photocatalytic material comprises a flexible substrate layer and SnO positioned on the flexible substrate layer2A seed layer located on the SnO2Ga on seed layer2O3Nanopillar array, the Ga2O3The nanopillar array is composed of a plurality of Ga2O3The nano-columns are arranged in a spaced array, and the Ga2O3The cross section of the nano-column is quadrilateral.
Wherein the Ga is2O3The height of the nano column is 1-2 mu m, and the diagonal length of the cross section is 80-500 nm.
Wherein the Ga is2O3the nano-column array is α -Ga2O3nanopillar array, α/β -Ga2O3combined with nano-column array or β -Ga2O3An array of nanopillars.
Preferably, the flexible substrate layer is a flexible glass fiber substrate.
The present invention also includes a second solution, as shown in FIG. 1, for preparing the above Ga based on flexible substrate2O3A method of nano-pillar photocatalytic material, comprising:
depositing a layer of SnO on a flexible substrate by radio frequency magnetron sputtering under vacuum2Film and annealing to form flexible substrate/SnO2A seed crystal layer;
bonding a Flexible substrate/SnO2A seed layer is arranged on Ga (NO)3)3In the water solution, carrying out hydrothermal reaction to form a GaOOH nano-column array;
calcining for 4 hours at 400 ℃ to obtain α -Ga2O3An array of nanopillars.
Further, it comprises carrying out a second calcination at 700 ℃ to form Ga2O3Nanopillar arrays, i.e.Obtaining Ga based on flexible substrate2O3The nano-pillar array is made of a photocatalytic material.
Wherein, the Ga (NO)3)3The concentration of the aqueous solution is 6.7-20mg/mL, the temperature of the hydrothermal reaction is 150 ℃, and the time of the hydrothermal reaction is 8-12 h.
Wherein the specific parameter of the radio frequency magnetron sputtering is that the vacuum degree of a cavity is 5 multiplied by 10-4Pa, working atmosphere Ar and O2Ar and O2The ratio of (1-2) to (1), the working pressure is 0.8Pa, the temperature of the flexible substrate is 550 ℃, the sputtering power is 100W, and the sputtering time is 4 h.
Wherein the annealing temperature is 550 ℃, and the annealing time is 2 h.
Wherein the flexible substrate/SnO2A seed layer is arranged on Ga (NO)3)3In the aqueous solution, the flexible substrate/SnO is2The seed crystal layer is fixed on the glass slide, and the glass slide and the flexible substrate/SnO are fixed on the glass slide2The seed crystal layer leans against the inner wall of the high-pressure reaction kettle, and then hydrothermal reaction is carried out.
Wherein the time of the secondary calcination is 20-120 min.
The flexible glass fiber substrate is subjected to pretreatment, namely ultrasonic cleaning is carried out on the flexible glass fiber substrate for 10min by respectively using acetone, absolute ethyl alcohol and deionized water, and then dry N is used2Air-dried and dried in an oven at 60 ℃ for 12 h.
For a better understanding of the present invention, the following are specific examples of the present invention.
Example 1
Ga based on flexible substrates2O3The preparation method of the nano-pillar photocatalytic material comprises the following steps:
(1) ultrasonic cleaning flexible glass fiber substrate with acetone, anhydrous ethanol and deionized water for 10min, and drying with dry N2Air drying, and drying in an oven at 60 deg.C for 12 h;
(2) depositing on the substrate cleaned in the step (1) in vacuum by a radio frequency magnetron sputtering technologyAccumulated SnO2The film is used as a growth seed layer and is annealed in a muffle furnace. The specific parameters of the used radio frequency magnetron sputtering technology are as follows: the vacuum degree of the cavity is 5 multiplied by 10-4Pa, working atmosphere Ar and O2The proportion is 1:1, the working pressure is 0.8Pa, the substrate temperature is 550 ℃, the sputtering power is 100W, and the sputtering time is 4 h; the parameters of the muffle annealing treatment used were as follows: the annealing temperature is 550 ℃, and the annealing time is 2 h.
(3) The sample obtained after the treatment of step (2) is placed in Ga (NO) of 0.2g/30mL3)3growing in a growth aqueous solution for 12h at 150 ℃ in a stainless steel high-pressure reaction kettle to obtain a GaOOH nano-column array, and then calcining in a muffle furnace for 4h at 400 ℃ to obtain α -Ga based on a flexible substrate2O3An array of nanopillars.
further comprises a step (4) of preparing α -Ga based on a flexible substrate2O3The nanopillar array is annealed at 700 deg.C for 20min, 30min, 40min, 60min, 90min and 120min respectively to obtain Ga of different phases2O3An array of nanopillars.
Ga prepared in step (3) and step (4) based on flexible substrate in the embodiment of the invention2O3The nano-pillar photocatalytic material comprises a flexible substrate layer and SnO positioned on the flexible substrate layer2A seed layer located on the SnO2Ga on seed layer2O3Nanopillar array, the Ga2O3The nanopillar array is composed of a plurality of Ga2O3The nano-columns are arranged in a spaced array, and the Ga2O3The cross section of the nano-column is quadrilateral, Ga2O3The height of the nano column is 1-2 mu m, and the diagonal length of the cross section is 80-500 nm.
the alpha-Ga obtained in the step (3)2O3When the nanopillar array is observed in a scanning electron microscope, as shown in fig. 2 and 3, it is found that the nanopillars grow uniformly, gaps exist between the nanopillars, the longest angular line of the cross section is 400nm, and the height of the nanopillars is about 2 μm.
In the embodiment of the invention, Ga is prepared on the flexible substrate by an in-situ synthesis method2O3Nanopillar array of which SnO2Seed layer as growth of Ga2O3The flexible glass fiber substrate of the catalyst of the nano-column array is an excellent inorganic non-metallic material and has the advantages of high strength, acid and alkali resistance, corrosion resistance, large specific surface and the like, so that the Ga based on the flexible substrate2O3When the nano-pillar array is used as a photocatalyst, the nano-pillar array is easy to recycle, has large photocatalytic specific surface area and can fully absorb light; and the preparation method is simple, green and environment-friendly, and easy for industrial production.
FIGS. 4 and 5 show Ga having different phase structures obtained in step (3) and step (4)2O3The XRD pattern and Raman pattern of the nanopillar array are combined to show that the Ga obtained in the step (3)2O3the nano-column array is α -Ga2O3nanopillar array, α -Ga2O3α/β -Ga can be obtained by the nano column array after annealing for 20-90min at 700 DEG C2O3the phase combination nano-column array is completely converted into β -Ga by further increasing the annealing time2O3An array of nanopillars.
Obtaining Ga of different phases from the step (3) and the step (4)2O3the nano-pillar array photocatalytic material is used for carrying out photocatalytic degradation performance test on the RhB aqueous solution under the irradiation of 254nm ultraviolet light, and as can be seen from figure 6, α -Ga2O3α/β -Ga obtained by annealing at 700 ℃ for 60min2O3the combined nano-column photocatalyst has the best photocatalytic performance due to the alpha/β -Ga2O3the phase combination nano-column is beneficial to the separation of photogenerated carriers, and figure 7 shows that α/β -Ga2O3under the existence of the phase-combination photocatalyst, the change of the absorption spectrum of the RhB aqueous solution in 60min of ultraviolet irradiation can be seen from the figure, and α/β -Ga based on the flexible substrate2O3The combined nano-column material has good photocatalytic performance.
Example 2
The steps (1) and (2) are the same as those in embodiment 1, and are not described herein again.
(3) The sample obtained after the treatment of step (2) is placed in 0.6g/30mL Ga (NO)3)3in the growth aqueous solution, the GaOOH nano-column array is obtained by growing for 8h at 150 ℃ in a stainless steel high-pressure reaction kettle, and then the GaOOH nano-column array is calcined for 4h at 400 ℃ in a muffle furnace to obtain the α -Ga2O3 nano-column array.
further comprises a step (4) of preparing α -Ga based on a flexible substrate2O3Annealing the nano-column array at 700 ℃ for 20min-120min to prepare Ga of different phases2O3An array of nanopillars. Obtained Ga2O3The chemical composition and the morphology of the nanopillar array are similar to those of example 1.
Example 3
The steps (1), (2) and (4) are the same as those in embodiment 1, and are not described herein again.
(3) The sample obtained after the treatment of the step (2) is placed in 0.3g/30mL Ga (NO)3)3growing in the growth aqueous solution for 10h at 150 ℃ in a stainless steel high-pressure reaction kettle to obtain a GaOOH nano-column array, and then calcining in a muffle furnace for 4h at 400 ℃ to obtain α -Ga2O3An array of nanopillars. Obtained Ga2O3The chemical composition and the morphology of the nanopillar array are similar to those of example 1.
Example 4
The steps (1), (3) and (4) are the same as those in embodiment 1, and are not described herein again.
(2) SnO is deposited on the substrate cleaned in the step (1) in vacuum through a radio frequency magnetron sputtering technology2The film is used as a growth seed layer and is annealed in a muffle furnace. The specific parameters of the used radio frequency magnetron sputtering technology are as follows: the vacuum degree of the cavity is 5 multiplied by 10-4Pa, working atmosphere Ar and O2The ratio is 2:1, the working pressure is 0.8Pa, the substrate temperature is 550 ℃, the sputtering power is 100W, and the sputtering time is 4 h; the parameters of the muffle annealing treatment used were as follows: the annealing temperature is 550 ℃, and the annealing time is 2 h.
Obtained Ga2O3The chemical composition and the morphology of the nanopillar array are similar to those of example 1.
Example 5
Step (1) is the same as in example 1 and will not be described herein again.
(2) SnO is deposited on the substrate cleaned in the step (1) in vacuum through a radio frequency magnetron sputtering technology2The film is used as a growth seed layer and is annealed in a muffle furnace. The specific parameters of the used radio frequency magnetron sputtering technology are as follows: the vacuum degree of the cavity is 5 multiplied by 10-4Pa, working atmosphere Ar and O2The ratio is 2:1, the working pressure is 0.8Pa, the substrate temperature is 550 ℃, the sputtering power is 100W, and the sputtering time is 4 h; the parameters of the muffle annealing treatment used were as follows: the annealing temperature is 550 ℃, and the annealing time is 2 h.
(3) The sample obtained after the treatment of step (2) is placed in Ga (NO) of 0.2g/30mL3)3growing in the growth aqueous solution for 10h at 150 ℃ in a stainless steel high-pressure reaction kettle to obtain a GaOOH nano-column array, and then calcining in a muffle furnace for 4h at 400 ℃ to obtain α -Ga2O3An array of nanopillars. Obtained Ga2O3The chemical composition and the morphology of the nanopillar array are similar to those of example 1.
Claims (10)
1. Ga based on flexible substrate2O3The nano-pillar photocatalytic material is characterized by comprising a flexible substrate layer and SnO positioned on the flexible substrate layer2A seed layer located on the SnO2Ga on seed layer2O3Nanopillar array, the Ga2O3The nanopillar array is composed of a plurality of Ga2O3The nano-columns are arranged in a spaced array, and the Ga2O3The cross section of the nano-column is quadrilateral.
2. Ga based on flexible substrates according to claim 12O3The nanopillar photocatalytic material is characterized in that the Ga2O3The height of the nano column is 1-2 mu m, and the diagonal length of the cross section is 80-500 nm.
3. Ga based on flexible substrates according to claim 12O3The nanopillar photocatalytic material is characterized in that the Ga2O3the nano-column array is α -Ga2O3nanopillar array, α/β -Ga2O3combined with nano-column array or β -Ga2O3An array of nanopillars.
4. Ga based on flexible substrates according to claim 12O3The nano-column photocatalytic material is characterized in that the flexible substrate layer is a flexible glass fiber substrate.
5. Preparation of Ga based on flexible substrates according to any one of claims 1 to 42O3The method for preparing the nano-pillar photocatalytic material is characterized by comprising the following steps:
depositing a layer of SnO on a flexible substrate by radio frequency magnetron sputtering under vacuum2Film and annealing to form flexible substrate/SnO2A seed crystal layer;
bonding a Flexible substrate/SnO2A seed layer is arranged on Ga (NO)3)3In the water solution, carrying out hydrothermal reaction to form a GaOOH nano-column array;
calcining for 4 hours at 400 ℃ to obtain α -Ga2O3nano-pillar array, namely α -Ga based on the flexible substrate2O3An array of nanopillars.
6. the method of claim 5, comprising providing a flexible substrate-based α -Ga2O3the nano-column array is calcined for the second time at 700 ℃, α/β -Ga2O3combined with nano-column array or β -Ga2O3An array of nanopillars.
7. A method according to claim 5 or 6, wherein said flexible substrate/SnO2A seed layer is arranged on Ga (NO)3)3In the aqueous solution, the flexible substrate/SnO is2The seed crystal layer is fixed on the glass slide, and the glass slide and the flexible substrate/SnO are fixed on the glass slide2The seed crystal layer leans against the inner wall of the high-pressure reaction kettle, and then hydrothermal reaction is carried out, wherein Ga (NO) is3)3The concentration of the aqueous solution is 6.7-20mg/mL, the temperature of the hydrothermal reaction is 150 ℃, and the time of the hydrothermal reaction is 8-12 h.
8. The preparation method according to claim 5 or 6, wherein the specific parameter of the RF magnetron sputtering is that the vacuum degree of the cavity is 5 x 10-4Pa, working atmosphere Ar and O2Ar and O2The ratio of (1-2) to (1), the working pressure is 0.8Pa, the temperature of the flexible substrate is 550 ℃, the sputtering power is 100W, and the sputtering time is 4 h.
9. The method according to claim 5 or 6, wherein the annealing temperature is 550 ℃ and the annealing time is 2 hours.
10. The method according to claim 6, wherein the time for the secondary calcination is 20 to 120 min.
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