CN109972202B - Preparation method of tungsten trioxide single crystal nanowire - Google Patents
Preparation method of tungsten trioxide single crystal nanowire Download PDFInfo
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002070 nanowire Substances 0.000 title claims abstract description 50
- 239000013078 crystal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 229910052786 argon Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
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- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- 238000002485 combustion reaction Methods 0.000 description 1
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- B82—NANOTECHNOLOGY
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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Abstract
The invention provides a preparation method of tungsten trioxide single crystal nanowires, which comprises the following steps: (1) placing a transparent conductive substrate in a low temperature zone of a tube furnace, WO2.9Placing the raw material powder in a high-temperature area of a tube furnace; (2) vacuumizing the tube furnace, and introducing mixed gas of oxygen and argon from the high-temperature area; (3) and (3) carrying out reaction under a heating condition, and obtaining the tungsten trioxide single crystal nanowire after the reaction is finished. The preparation method utilizes a double-temperature-zone chemical vapor deposition method, carries the raw material gasified in a high-temperature zone to a low-temperature zone through airflow, and deposits and grows WO with a specific nano structure on a substrate3The prepared tungsten trioxide single crystal nanowire as a photoanode shows excellent photoelectrochemical properties.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and relates to a preparation method of tungsten trioxide single crystal nanowires.
Background
Photoelectrochemical water splitting is one of the world recognized important ways to address the global energy crisis. The hydrogen generated by the light-driven water decomposition is clean energy, and the water generated by the hydrogen combustion can be used as the raw material for preparing the hydrogen again, so that the photoelectrochemistry water decomposition technology can realize the effective utilization of solar energy and is expected to promote the sustainable development of the society. The basic principle is that the light-excited semiconductor generates electrons and holes which are respectively used for two half reactions of water reduction hydrogen generation and water oxidation oxygen generation. The oxygen production reaction is more difficult than the hydrogen production reaction and is a restriction step in the water decomposition process of photoelectrochemistry, so that the development of a high-performance photo-anode for the oxygen production half reaction is very critical to the popularization and application of the technology.
Tungsten trioxide (WO)3) The N-type semiconductor is an n-type semiconductor with low price, high conductivity and good stability, and is a photo-anode material with great potential. In recent years, the development of nanotechnology has brought about the art of photoelectrochemistry as an eoscopy, and it has been reported that a nanowire-structured photoelectrode has excellent charge separation efficiency. However high performance WO3The development of nanowire photoanodes still presents some challenges. First, WO3Growing on transparent conductive glass substrate to narrowThe band-gap photocathodes are connected in series to form a device for decomposing water by full light; however, since the transparent conductive glass substrate cannot withstand high temperature, WO is grown on the surface thereof3Nanowires are difficult. On the other hand, the photoelectrochemical property is sensitive to the length of the nanowire, the overlong nanowire brings larger charge transmission resistance, and the overlong nanowire is not beneficial to the full absorption of the light energy, so that the control of the length of the nanowire is very critical. In addition, lattice defects in the nanowires can induce electron-hole recombination, thereby reducing the utilization rate of photo-generated charges, and thus, the crystallinity of the nanowires needs to be improved. To solve the above problems, we have invented a WO growth length adjustable on transparent conductive glass3A method for preparing a single crystal nanowire array.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method of tungsten trioxide single crystal nanowires, which utilizes a dual-temperature-zone chemical vapor deposition method to carry the gasified raw material in a high-temperature zone to a low-temperature zone through airflow, and the raw material is deposited and grown on a substrate to form WO with a specific nanostructure3The prepared tungsten trioxide single crystal nanowire as a photoanode shows excellent photoelectrochemical properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of tungsten trioxide single crystal nanowires, which comprises the following steps:
(1) placing a transparent conductive substrate in a low-temperature region of a tube furnace, and placing elemental tungsten or tungsten oxide raw material powder in a high-temperature region of the tube furnace;
(2) vacuumizing the tube furnace, and introducing mixed gas of oxygen and argon from the high-temperature area;
(3) and (3) carrying out reaction under a heating condition, and obtaining the tungsten trioxide single crystal nanowire after the reaction is finished.
In the invention, the transparent conductive substrate can be cut and cleaned before the step (1), and the cutting size can be adjusted according to the requirement of a prepared sample and the size of a tube furnace; the cleaning method comprises sequentially performing ultrasonic treatment in isopropanol, acetone and ethanol for 15min, and blowing with nitrogen. However, the method is not limited to the above cleaning method, and any method for cleaning the transparent conductive substrate used in the present invention is applicable to the present invention.
As a preferred technical scheme of the invention, the transparent conductive substrate comprises F-doped SnO2(FTO) or In-doped SnO2(ITO) transparent conductive glass.
Preferably, the tungsten oxide comprises WO2.9And/or WO3。
In a preferred embodiment of the present invention, the distance between the high temperature region and the low temperature region is 35 to 36cm, such as 35.1cm, 35.2cm, 35.3cm, 35.4cm, 35.5cm, 35.6cm, 35.7cm, 35.8cm or 35.9cm, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In the invention, the distance between the high-temperature area and the low-temperature area is actually the distance between two lower heating sources of the tube furnace, and the ideal appearance can be obtained by placing the raw material/substrate in the center of the heat source. When the raw material is fixed in the center of a heat source of a high-temperature area, if the distance between the substrate and the heat source is too short, the shape of the nanosheet can be obtained; if the substrate is too far from it, it may result in low nanowire density or bending of the nanowires.
In a preferred embodiment of the present invention, the pressure in the tube furnace after evacuation is 0.17 to 0.20 torr, for example, 0.175 torr, 0.18 torr, 0.185 torr, 0.19 torr, or 0.195 torr, but the pressure is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
In a preferred embodiment of the present invention, the flow rate of the oxygen gas is 5 to 15sccm, such as 6sccm, 7sccm, 8sccm, 9sccm, 10sccm, 11sccm, 12sccm, 13sccm, or 14sccm, but the flow rate is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the flow rate of argon is 350-400 sccm, such as 360sccm, 370sccm, 380sccm, or 390sccm, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
The inventionIn addition, argon is used as a carrier gas, and the influence on the final product is not obvious. The actual effect is that Ar and O2When the flow rate of argon is fixed, too high oxygen flow rate results in low nanowire density, and too low oxygen flow rate results in crystal defects.
As a preferable technical scheme of the invention, the outlet of the low-temperature area is provided with a vacuum pump for vacuumizing and forming a reaction environment for gas flowing.
In a preferred embodiment of the present invention, the temperature of the high temperature region is 940 to 1100 ℃, such as 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃ or 1090 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
Preferably, the temperature of the low temperature region is 300 to 400 ℃, such as 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃ or 390 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the high-temperature area and the low-temperature area are heated simultaneously.
Preferably, the temperature increase rate is 15-25 deg.C/min, such as 16 deg.C/min, 17 deg.C/min, 18 deg.C/min, 19 deg.C/min, 20 deg.C/min, 21 deg.C/min, 22 deg.C/min, 23 deg.C/min, or 24 deg.C/min, but is not limited to the values listed, and other values not listed within the range of values are equally applicable.
In a preferred embodiment of the present invention, the reaction time is 90 to 120min, such as 95min, 100min, 105min, 110min or 115min, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In the invention, the method for taking out the sample after the reaction is finished comprises the following steps: and keeping the airflow, closing the airflow after the furnace temperature is reduced to the room temperature, closing the vacuum pump, communicating with the atmosphere, and taking out the sample.
As a preferable technical scheme of the invention, the preparation method of the tungsten trioxide single crystal nanowire comprises the following steps:
(1) placing a transparent conductive substrate in a low temperature zone of a tube furnace, WO2.9Placing the raw material powder in a high-temperature area of a tube furnace, wherein the distance between the high-temperature area and the low-temperature area is 35-36 cm;
(2) a vacuum pump is arranged at an outlet of the low-temperature area to vacuumize the tubular furnace until the pressure in the tubular furnace is 0.17-0.20 Torr, mixed gas of oxygen and argon is introduced from the high-temperature area, the flow of the oxygen is 10-15 sccm, and the flow rate of the argon is 350-400 sccm;
(3) and simultaneously heating the high-temperature area and the low-temperature area, wherein the heating rate is 15-25 ℃/min, the temperature of the high-temperature area is 940-1100 ℃, the temperature of the low-temperature area is 300-400 ℃, reacting for 90-120 min under a heating condition, and obtaining the tungsten trioxide single crystal nanowire after the reaction is finished.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the preparation method of the tungsten trioxide single crystal nanowire, the two-temperature-region chemical vapor deposition method is utilized, the raw material is placed in the high-temperature region, and the substrate is placed in the low-temperature region, so that the problem that the transparent conductive substrate cannot resist high temperature is effectively solved;
(2) the preparation method of the tungsten trioxide single crystal nanowire can prepare high-density WO with uniform appearance3The monocrystal nanowire array used as a photoanode shows excellent photoelectrochemical performance, and the photocurrent of the monocrystal nanowire array under 1.23V vs. RHE can reach 0.93mA cm-2。
Drawings
FIG. 1 shows the growth of WO3A schematic diagram of a tube furnace used for the single crystal nanowire, a corresponding temperature zone and an airflow direction;
FIG. 2 is WO3Scanning electron microscope images of nanowire array cross-sections;
FIG. 3 is WO3A transmission electron microscope image of the single crystal nanowire and a corresponding selected area electron diffraction image thereof;
FIG. 4 shows WO with a large number of lattice defects3Transmission electron microscope images of the nanowires and their corresponding selected area electron diffraction patterns.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method of a tungsten trioxide single crystal nanowire, which comprises the following steps:
(1) placing the FTO substrate in a low temperature zone of a tube furnace, WO2.9Placing the raw material powder in a high-temperature area of a tube furnace, wherein the distance between the high-temperature area and the low-temperature area is 35 cm;
(2) closing the tubular furnace body, screwing screws at two ends, starting a vacuum pump arranged at an outlet of the low-temperature region, reducing the air pressure in the tubular furnace to 0.17-0.20 torr, and introducing mixed gas of oxygen and argon from the high-temperature region, wherein the flow of the oxygen is 15sccm, and the flow rate of the argon is 400 sccm;
(3) and simultaneously heating the high-temperature area and the low-temperature area, wherein the heating rate is 20 ℃/min, the temperature of the high-temperature area is 1100 ℃, the temperature of the low-temperature area is 350 ℃, reacting for 90min under a heating condition, keeping airflow after the reaction is finished, closing the airflow after the furnace temperature is reduced to room temperature, then closing a vacuum pump, communicating with the atmosphere, and taking out a sample to obtain the tungsten trioxide single crystal nanowire.
In this example, FTO was cut at 2cm x 1.5cm size before step (1), sonicated in isopropanol, acetone, ethanol for 15min each in turn, and then blown dry with nitrogen.
Example 2
The embodiment provides a preparation method of a tungsten trioxide single crystal nanowire, which comprises the following steps:
(1) placing the FTO substrate in a tube furnaceLow temperature zone, WO2.9Placing the raw material powder in a high-temperature area of a tube furnace, wherein the distance between the high-temperature area and the low-temperature area is 35 cm;
(2) closing the tubular furnace body, screwing screws at two ends, starting a vacuum pump arranged at an outlet of the low-temperature region, reducing the air pressure in the tubular furnace to 0.17-0.20 torr, and introducing mixed gas of oxygen and argon from the high-temperature region, wherein the flow of the oxygen is 15sccm, and the flow rate of the argon is 400 sccm;
(3) and simultaneously heating the high-temperature area and the low-temperature area, wherein the heating rate is 20 ℃/min, the temperature of the high-temperature area is 1100 ℃, the temperature of the low-temperature area is 350 ℃, reacting for 120min under a heating condition, keeping airflow after the reaction is finished, closing the airflow after the furnace temperature is reduced to room temperature, then closing a vacuum pump, communicating with the atmosphere, and taking out a sample to obtain the tungsten trioxide single crystal nanowire.
In this example, FTO was cut at 2cm x 1.5cm size before step (1), sonicated in isopropanol, acetone, ethanol for 15min each in turn, and then blown dry with nitrogen.
Example 3
The embodiment provides a preparation method of a tungsten trioxide single crystal nanowire, which comprises the following steps:
(1) placing the FTO substrate in a low temperature zone of a tube furnace, WO2.9Placing the raw material powder in a high-temperature area of a tube furnace, wherein the distance between the high-temperature area and the low-temperature area is 35 cm;
(2) closing the tubular furnace body, screwing screws at two ends, starting a vacuum pump arranged at an outlet of the low-temperature region, reducing the air pressure in the tubular furnace to 0.17-0.20 torr, and introducing mixed gas of oxygen and argon from the high-temperature region, wherein the flow rate of the oxygen is 8sccm, and the flow rate of the argon is 400 sccm;
(3) and simultaneously heating the high-temperature area and the low-temperature area, wherein the heating rate is 20 ℃/min, the temperature of the high-temperature area is 1100 ℃, the temperature of the low-temperature area is 350 ℃, reacting for 90min under a heating condition, keeping airflow after the reaction is finished, closing the airflow after the furnace temperature is reduced to room temperature, then closing a vacuum pump, communicating with the atmosphere, and taking out a sample to obtain the tungsten trioxide single crystal nanowire.
In this example, FTO was cut at 2cm x 1.5cm size before step (1), sonicated in isopropanol, acetone, ethanol for 15min each in turn, and then blown dry with nitrogen.
Example 4
The embodiment provides a preparation method of a tungsten trioxide single crystal nanowire, which comprises the following steps:
(1) placing the FTO substrate in a low temperature zone of a tube furnace, WO2.9Placing the raw material powder in a high-temperature area of a tube furnace, wherein the distance between the high-temperature area and the low-temperature area is 35 cm;
(2) closing the tubular furnace body, screwing screws at two ends, starting a vacuum pump arranged at an outlet of the low-temperature region, reducing the air pressure in the tubular furnace to 0.17-0.20 torr, and introducing mixed gas of oxygen and argon from the high-temperature region, wherein the flow of the oxygen is 5sccm, and the flow rate of the argon is 400 sccm;
(3) and simultaneously heating the high-temperature area and the low-temperature area, wherein the heating rate is 20 ℃/min, the temperature of the high-temperature area is 1100 ℃, the temperature of the low-temperature area is 350 ℃, reacting for 90min under a heating condition, keeping airflow after the reaction is finished, closing the airflow after the furnace temperature is reduced to room temperature, then closing a vacuum pump, communicating with the atmosphere, and taking out a sample to obtain the tungsten trioxide single crystal nanowire.
In this example, FTO was cut at 2cm x 1.5cm size before step (1), sonicated in isopropanol, acetone, ethanol for 15min each in turn, and then blown dry with nitrogen.
Example 5
The embodiment provides a preparation method of a tungsten trioxide single crystal nanowire, which comprises the following steps:
(1) placing the FTO substrate in a low temperature zone of a tube furnace, WO2.9Placing the raw material powder in a high-temperature area of a tube furnace, wherein the distance between the high-temperature area and the low-temperature area is 36 cm;
(2) closing the tubular furnace body, screwing screws at two ends, starting a vacuum pump arranged at an outlet of the low-temperature region, reducing the air pressure in the tubular furnace to 0.17-0.20 torr, and introducing mixed gas of oxygen and argon from the high-temperature region, wherein the flow of the oxygen is 5sccm, and the flow rate of the argon is 400 sccm;
(3) and simultaneously heating the high-temperature area and the low-temperature area, wherein the heating rate is 25 ℃/min, the temperature of the high-temperature area is 1100 ℃, the temperature of the low-temperature area is 350 ℃, reacting for 120min under a heating condition, keeping airflow after the reaction is finished, closing the airflow after the furnace temperature is reduced to room temperature, then closing a vacuum pump, communicating with the atmosphere, and taking out a sample to obtain the tungsten trioxide single crystal nanowire.
In this example, before step (1), ITO was cut in a size of 2cm x 1.5cm, sequentially sonicated in isopropanol, acetone, ethanol for 15min each, and then blown dry with nitrogen.
Comparative example
The comparative example provides a preparation method of a tungsten trioxide rice noodle with more lattice defects, and the preparation method comprises the following steps:
(1) placing the FTO substrate in a low temperature zone of a tube furnace, WO2.9Placing the raw material powder in a high-temperature area of a tube furnace, wherein the distance between the high-temperature area and the low-temperature area is 36 cm;
(2) closing the tubular furnace body, screwing screws at two ends, starting a vacuum pump arranged at an outlet of the low-temperature region, reducing the air pressure in the tubular furnace to 0.17-0.20 torr, and introducing mixed gas of oxygen and argon from the high-temperature region, wherein the flow of the oxygen is 2.5sccm, and the flow rate of the argon is 400 sccm;
(3) and simultaneously heating the high-temperature area and the low-temperature area, wherein the heating rate is 15 ℃/min, the temperature of the high-temperature area is 1100 ℃, the temperature of the low-temperature area is 350 ℃, reacting for 90min under a heating condition, keeping airflow after the reaction is finished, closing the airflow after the furnace temperature is reduced to room temperature, then closing a vacuum pump, communicating with the atmosphere, and taking out a sample to obtain the tungsten trioxide nanowire.
In this example, FTO was cut at 2cm x 1.5cm size before step (1), sonicated in isopropanol, acetone, ethanol for 15min each in turn, and then blown dry with nitrogen.
Photoelectrochemical property test:
testing of WO Using a three-electrode System3The photoelectrochemical property of the nanowire array photoanode is that Pt is used as a counter electrode and Ag/AgCl is used as a reference electrode. WO3The contact area of the nanowire photoelectric anode and the electrolyte is 0.636 square centimeter, the light source is simulated solar light, the sample is irradiated from the front side, and 0.5M Na is used2SO4As an electrolyte. Comparing the performance of the photo-anode with the photocurrent of 1.23V vs. rhe, the larger the photocurrent, the better the performance, and the test results are shown in table 1:
TABLE 1
From the test results of Table 1, it can be seen that O2The flow rate has a large impact on the sample performance because the oxygen flow rate has a significant impact on the crystallinity of the nanowires. The 15sccm samples (examples 1 and 2) were the highest performing single crystal nanowires (as shown in figure 3), and the 2.5sccm samples (comparative) had more lattice defects (as shown in figure 4) and the lowest performing.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (4)
1. A preparation method of tungsten trioxide single crystal nanowires is characterized by comprising the following steps:
(1) placing a transparent conductive substrate in a low-temperature region of a tube furnace, placing elemental tungsten or tungsten oxide raw material powder in a high-temperature region of the tube furnace, wherein the distance between the high-temperature region and the low-temperature region is 35-36 cm;
wherein the transparent conductive substrate comprises F-doped SnO2Or In-doped SnO2Transparent conductive glass;
(2) vacuumizing the tube furnace, wherein the air pressure in the tube furnace after vacuumizing is 0.17-0.20 torr, and introducing mixed gas of oxygen and argon from the high-temperature region, wherein the flow of the oxygen is 5-15 sccm, and the flow of the argon is 350-400 sccm;
(3) carrying out reaction under a heating condition, wherein the temperature of the high-temperature region is 940-1100 ℃, the temperature of the low-temperature region is 300-400 ℃, and obtaining the tungsten trioxide single crystal nanowire after the reaction is finished;
the temperature of the high-temperature area and the temperature of the low-temperature area are simultaneously raised, the temperature raising rate of the high-temperature area and the temperature raising rate of the low-temperature area are respectively and independently 15-25 ℃/min, and the reaction time is 90-120 min.
2. The method of claim 1, wherein the tungsten oxide comprises WO2.9And/or WO3。
3. The preparation method according to claim 1, wherein the low temperature zone outlet is provided with a vacuum pump for vacuum pumping and a reaction environment for forming gas flow.
4. The production method according to any one of claims 1 to 3, characterized by comprising the steps of:
(1) placing a transparent conductive substrate in a low temperature zone of a tube furnace, WO2.9Placing the raw material powder in a high-temperature area of a tube furnace, wherein the distance between the high-temperature area and the low-temperature area is 35-36 cm;
(2) a vacuum pump is arranged at an outlet of the low-temperature area to vacuumize the tubular furnace until the pressure in the tubular furnace is 0.17-0.20 Torr, mixed gas of oxygen and argon is introduced from the high-temperature area, the flow of the oxygen is 5-15 sccm, and the flow rate of the argon is 350-400 sccm;
(3) and simultaneously heating the high-temperature area and the low-temperature area, wherein the heating rate is 15-25 ℃/min, the temperature of the high-temperature area is 940-1100 ℃, the temperature of the low-temperature area is 300-400 ℃, reacting for 90-120 min under a heating condition, and obtaining the tungsten trioxide single crystal nanowire after the reaction is finished.
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