CN109999881B - N-doped orthorhombic phase III main group chalcogenide and preparation method - Google Patents
N-doped orthorhombic phase III main group chalcogenide and preparation method Download PDFInfo
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- 150000004770 chalcogenides Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 229910052786 argon Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910005543 GaSe Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical group CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000004518 low pressure chemical vapour deposition Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000004506 ultrasonic cleaning Methods 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 21
- 239000011669 selenium Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Abstract
The invention discloses an N-doped orthorhombic phase III main group chalcogenide and a preparation method thereof, which comprises the steps of carrying out ultrasonic cleaning and high-temperature annealing treatment on a silver foil substrate, synthesizing an N-doped III main group chalcogenide sheet with uniform size by using a low-pressure chemical vapor deposition method in a nitrogen-containing atmosphere, keeping the reaction temperature for 10-20 minutes, and stopping introducing argon and ammonia gas when naturally cooling to the room temperature, thereby obtaining an N-doped orthorhombic phase III main group chalcogenide thin layer sample with uniform size on the silver foil substrate. The chemical vapor deposition method used by the method can realize large-scale and high-quality N-doped orthorhombic phase III main group chalcogenide flakes, has simple preparation process, can realize large-scale mass production, and is expected to be applied to the field of photocatalysis.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to an N-doped orthorhombic phase III main group chalcogenide and a preparation method thereof.
Background
Energy is the material basis on which human beings live and develop, and is also an important strategic resource for national economic development. The total amount of primary energy supply in the world has increased almost 2.5 times during 1971 to 2016, and fossil fuels still dominate the supply of primary energy. The development and utilization of these fossil energy resources in large quantities has led to an increasingly severe energy shortage due to the limited storage capacity thereof, while driving the rapid development of the world economy. Meanwhile, the combustion of these fossil fuels emits a large amount of harmful substances of exhaust gas and waste residues, resulting in environmental pollution, and human beings are facing increasingly serious problems of energy shortage and environmental destruction. Therefore, saving energy resources, protecting the environment, and developing and utilizing renewable energy sources have become the inevitable choices for human beings to realize sustainable development. While hydrogen energy is considered as the most promising clean fuel for future development, solar hydrogen production in water is more attractive and realistic.
The premise for realizing the application prospect research is that the large-scale and high-quality photocatalytic material can be prepared to participate in solar hydrogen production. Among these, two-dimensional group iii chalcogenides are attracting attention as two-dimensional photocatalytic materials that have recently emerged. The N-doped orthorhombic phase two-dimensional III main group chalcogenide can improve the atom adsorption capacity and has potential application in the field of photocatalysis. Currently, no economical and efficient method is available for the preparation of N-doped orthorhombic phase two-dimensional group iii chalcogenides. Therefore, how to realize large-scale preparation of N-doped orthogonal-phase two-dimensional group iii chalcogenide is a problem to be solved.
Disclosure of Invention
The invention provides a preparation method of an N-doped orthorhombic phase III main group chalcogenide, which is used for preparing an N-doped orthorhombic phase III main group chalcogenide sheet by a chemical vapor deposition method, wherein the N-doped orthorhombic phase III main group chalcogenide sheet is formed by any one of InSe, InS, GaSe and GaS under an argon atmosphere.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of making an N-doped orthorhombic phase group III chalcogenide comprising the steps of:
(1) respectively placing the precursor and the silver foil substrate in a high-temperature tube furnace with three temperature areas in sequence according to the airflow direction; wherein, one of S source and Se source, one of In source and Ga source, and silver foil substrate are placed In the three temperature zones In sequence;
(2) pumping the vacuum degree of the reaction cavity to about 6KPa, and introducing argon to clean the reaction cavity of the high-temperature tubular furnace;
(3) introducing argon and ammonia GaS, heating a high-temperature tube furnace with three temperature zones simultaneously, and depositing the N generated by the reaction on the silver foil substrate by doping any one of InSe, InS, GaSe and GaS.
(4) Naturally cooling to room temperature, and simultaneously closing the introduction of argon and ammonia gas to obtain the N-doped orthorhombic phase III main group chalcogenide on the silver foil substrate.
Further, the silver foil substrate in the step (1) is pre-treated, and the method comprises the steps of putting the silver foil substrate into NaOH solution for cleaning, then carrying out ultrasonic cleaning in deionized water solution, and then carrying out high-temperature pre-annealing treatment on the cleaned substrate.
Further, argon gas with the flow rate of 50-60sccm and ammonia gas with the flow rate of 10-30sccm are introduced in the step (3);
further, the S source in the step (1) is S powder; the Se source is Se powder; the In source is powder In2O3(ii) a The Ga source is triethyl gallium.
Further, the heating temperature of the S source in the step (3) is 170-200 ℃; the heating temperature of the Se source is 240-270 ℃; the heating temperature of the In source is 610-640 ℃; the heating temperature of the Ga source is 80-110 ℃; the heating temperature of the silver foil substrate is 660-690 ℃.
In the invention, the preparation method of the N-doped orthorhombic phase III main group chalcogenide mainly comprises the following steps: mixing S/Se powder and powder In2O3And the silver foil substrate is sequentially and respectively placed in the three-temperature-zone tube furnace according to the airflow direction.
In the invention, the preparation method of the N-doped orthorhombic phase III main group chalcogenide mainly comprises the following steps: and respectively placing the liquid triethyl gallium, the S/Se powder and the silver foil substrate in a three-temperature-zone tubular furnace in sequence according to the airflow direction.
Further, the reaction in the step (4) is 10-20 min.
The invention has the beneficial effects that: the method for preparing the N-doped orthorhombic phase III main group chalcogenide is simple in preparation process and easy to scale, and the obtained N-doped orthorhombic phase III main group chalcogenide is expected to be applied to the field of photocatalysis in the future.
Drawings
FIG. 1 is a flow chart of the preparation of N-doped InS materials;
FIG. 2 is an XRD pattern of the N-doped InS material obtained in example 1;
FIG. 3 is an XRD pattern of an undoped N-doped InS material;
FIG. 4 is a SEM image of the N-doped InS material obtained in example 1;
FIG. 5 is a graph comparing the optical absorption coefficients of N-doped InS and undoped InS materials;
FIG. 6 is an XRD pattern of the materials obtained in examples 2-4.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
A method for preparing a two-dimensional N-doped InS material by adopting a low-pressure chemical vapor deposition method comprises the following specific steps:
(1) the silver foil was washed by placing in a solution of sodium hydroxide (0.5 mol/L), followed by ultrasonic washing in deionized water for 5 minutes. Carrying out pre-annealing treatment on the cleaned silver foil in a high-temperature annealing furnace at 900 ℃, wherein the annealing time is 3 hours;
(2) 1g of sulfur powder, 4g of indium oxide and 10 silver foil substrates are respectively placed in a three-temperature-zone tube furnace according to the airflow direction, wherein the distance between the silver foil substrates is 1 cm.
(3) Pumping the vacuum degree of the tubular furnace to 6KPa, and introducing argon at the flow rate of 60sccm to clean the reaction cavity;
(4) argon gas with the flow rate of 60sccm and ammonia gas with the flow rate of 30sccm are introduced, the temperature of the three-temperature-zone tubular furnace is simultaneously heated to 200 ℃, 640 ℃ and 690 ℃ within 20min, and the heating is stopped after the temperature is kept for 15min under the action of the gas flow;
(5) and naturally cooling to room temperature, and simultaneously closing argon and ammonia gas to obtain the N-doped InS material.
As can be seen from the XRD patterns of fig. 2 and 3, the doped InS and undoped InS materials are similar in peak shape, but differ slightly in the intensity of the diffraction peaks. Fig. 4 is a graph comparing the optical absorption coefficients of N-doped InS and undoped InS materials, with distinct absorption peaks in both the visible region, and in the ultraviolet region, which forms a continuum plateau corresponding to a direct interband transition between the valence and conduction bands. This means that both show excellent light capturing capabilities throughout the visible solar spectrum. However, in general, the absorption peak of the former is slightly higher than that of the latter in the visible light region, the absorption capacity of the former is also slightly stronger than that of the latter in the ultraviolet region, and the light absorption performance of the N-doped InS material is actually improved.
Example 2
A method for preparing a two-dimensional N-doped InSe material by adopting a low-pressure chemical vapor deposition method comprises the following specific steps:
(1) the silver foil was washed by placing in a solution of sodium hydroxide (0.5 mol/L), followed by ultrasonic washing in deionized water for 5 minutes. Carrying out pre-annealing treatment on the cleaned silver foil in a high-temperature annealing furnace at 900 ℃, wherein the annealing time is 3 hours;
(2) 1g of selenium powder, 2g of indium oxide and 10 silver foil substrates are respectively placed in a three-temperature-zone tube furnace according to the airflow direction, wherein the distance between the silver foil substrates is 1 cm.
(3) Pumping the vacuum degree of the tubular furnace to 6KPa, and introducing argon at the flow rate of 50sccm to clean the reaction cavity;
(4) introducing argon gas with the flow rate of 50sccm and ammonia gas with the flow rate of 20sccm, simultaneously heating the temperature of the three-temperature-zone tubular furnace to 240 ℃, 610 ℃ and 660 ℃ within 20min, keeping the temperature for 15min under the action of the gas flow, and stopping heating;
(5) and naturally cooling to room temperature, and simultaneously closing argon and ammonia gas to obtain the N-doped InSe material.
Example 3
A method for preparing a two-dimensional N-doped GaSe material by adopting a low-pressure chemical vapor deposition method comprises the following specific steps:
(1) the silver foil was washed by placing in a solution of sodium hydroxide (0.5 mol/L), followed by ultrasonic washing in deionized water for 5 minutes. Carrying out pre-annealing treatment on the cleaned silver foil in a high-temperature annealing furnace at 900 ℃, wherein the annealing time is 3 hours;
(2) 2g of triethyl gallium, 1g of selenium powder and 10 silver foil substrates are respectively placed in a three-temperature-zone tube furnace according to the airflow direction, wherein the distance between the silver foil substrates is 1 cm.
(3) Pumping the vacuum degree of the tubular furnace to 6KPa, and introducing argon at the flow rate of 60sccm to clean the reaction cavity;
(4) introducing argon gas with the flow rate of 60sccm and ammonia gas with the flow rate of 20sccm, simultaneously heating the temperature of the three-temperature-zone tubular furnace to 110 ℃, 260 ℃ and 660 ℃ within 20min, keeping the temperature for 15min under the action of the gas flow, and stopping heating;
(5) and naturally cooling to room temperature, and simultaneously closing argon and ammonia gas to obtain the N-doped GaSe material.
Example 4
A method for preparing a two-dimensional N-doped GaS material by adopting a low-pressure chemical vapor deposition method comprises the following specific steps:
(1) the silver foil was washed by placing in a solution of sodium hydroxide (0.5 mol/L), followed by ultrasonic washing in deionized water for 5 minutes. Carrying out pre-annealing treatment on the cleaned silver foil in a high-temperature annealing furnace at 900 ℃, wherein the annealing time is 3 hours;
(2) 5g of triethyl gallium, 1g of sulfur powder and 10 silver foil substrates are respectively placed in a three-temperature-zone tube furnace according to the airflow direction, wherein the distance between the silver foil substrates is 1 cm.
(3) Pumping the vacuum degree of the tubular furnace to 6KPa, and introducing argon at the flow rate of 50sccm to clean the reaction cavity;
(4) introducing argon gas with the flow rate of 50sccm and ammonia gas with the flow rate of 10sccm, simultaneously heating the temperature of the three-temperature-zone tubular furnace to 80 ℃, 200 ℃ and 690 ℃ within 20min, keeping the temperature for 15min under the action of the gas flow, and stopping heating;
(5) and naturally cooling to room temperature, and simultaneously closing argon and ammonia GaS to obtain the N-doped GaS material.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A method of making an N-doped orthorhombic phase group iii chalcogenide, comprising: preparing an N-doped orthorhombic phase III main group chalcogenide by adopting a chemical vapor deposition method, wherein the chalcogenide is any one of N-doped InSe, InS, GaSe and GaS generated in an argon atmosphere; the method comprises the following steps:
(1) respectively placing the precursor and the silver foil substrate in a high-temperature tube furnace with three temperature areas according to the airflow direction; wherein, one of S source and Se source, one of In source and Ga source, silver foil substrate are respectively placed In the three temperature zones;
(2) pumping the vacuum degree of the reaction cavity to 6KPa, and introducing argon to clean the reaction cavity of the high-temperature tubular furnace;
(3) introducing argon and ammonia GaS, heating a high-temperature tube furnace with three temperature zones simultaneously, reacting to generate any one of N-doped InSe, InS, GaSe and GaS, and depositing on the silver foil substrate;
(4) naturally cooling to room temperature, and simultaneously closing argon and ammonia gas to obtain the N-doped orthorhombic phase III main group chalcogenide on the silver foil substrate.
2. The method according to claim 1, wherein the silver foil substrate of step (1) is pre-treated, and comprises the steps of washing the silver foil substrate in NaOH solution, then ultrasonically washing the silver foil substrate in deionized water solution, and then pre-annealing the washed substrate at a high temperature.
3. The production method according to claim 1, wherein the flow rates of argon gas and ammonia gas introduced in the step (2) are 50 to 60sccm and 10 to 30sccm, respectively.
4. The method according to claim 1, wherein the S source of step (1) is S powder; the Se source is Se powder; the In source is powder In2O3(ii) a The Ga source is triethyl gallium.
5. The method as claimed in claim 1, wherein the heating temperature of the S source in the step (3) is 170-200 ℃; the heating temperature of the Se source is 240-270 ℃; the heating temperature of the In source is 610-640 ℃; the heating temperature of the Ga source is 80-110 ℃, and the heating temperature of the silver foil substrate is 660-690 ℃.
6. The method according to claim 1, wherein the reaction time of the step (4) is 10 to 20 min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726936A (en) * | 2015-03-27 | 2015-06-24 | 扬州大学 | Method for preparing orthogonal-phase MoO3 monocrystal nanosheet through chemical vapor deposition |
| CN105420815A (en) * | 2016-01-07 | 2016-03-23 | 中国科学院理化技术研究所 | Controllable method for preparing orthogonal-phase stannous sulfide two-dimensional monocrystalline nanosheet |
| CN105887045A (en) * | 2015-02-16 | 2016-08-24 | 炬力奈米科技有限公司 | Method And Apparatus For Fabricating Two-Dimensional Layered Chalcogenide Film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105887045A (en) * | 2015-02-16 | 2016-08-24 | 炬力奈米科技有限公司 | Method And Apparatus For Fabricating Two-Dimensional Layered Chalcogenide Film |
| CN104726936A (en) * | 2015-03-27 | 2015-06-24 | 扬州大学 | Method for preparing orthogonal-phase MoO3 monocrystal nanosheet through chemical vapor deposition |
| CN105420815A (en) * | 2016-01-07 | 2016-03-23 | 中国科学院理化技术研究所 | Controllable method for preparing orthogonal-phase stannous sulfide two-dimensional monocrystalline nanosheet |
Non-Patent Citations (1)
| Title |
|---|
| "Transport properties of nitrogen doped p-gallium selenide single crystals";19960101;《J. Appl. Phys.》;19960101;第79卷(第1期);第204页，II实验 * |
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