CN112626497B - Preparation method of SbOCl material based on ALD technology - Google Patents

Preparation method of SbOCl material based on ALD technology Download PDF

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CN112626497B
CN112626497B CN202011372261.8A CN202011372261A CN112626497B CN 112626497 B CN112626497 B CN 112626497B CN 202011372261 A CN202011372261 A CN 202011372261A CN 112626497 B CN112626497 B CN 112626497B
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杜立永
何冬梅
丁玉强
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Jiangnan University
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Abstract

The invention discloses a preparation method of an SbOCl material based on an ALD (atomic layer deposition) technology, belonging to the field of nano materials. Alternately leading the vaporized Sb source SbCl to be in vacuum3Introducing oxygen source water into a reaction cavity of Atomic Layer Deposition (ALD) equipment placed in advance into a substrate in a pulse mode, wherein the alternating pulse mode is as follows: SbCl3Pulse t1→ cleaning t2Pulse of water t →3→ cleaning t4Completing a single growth cycle in this mode; and repeating a plurality of single growth cycles at a specific deposition temperature to obtain the sediment with the SbOCl material. The invention adopts SbCl3The combination of the SbOCl material and oxygen source water is further applied to an atomic layer deposition technology, so that the SbOCl material with controllable loading capacity and atomic active site distribution and photocatalytic performance can be deposited on various substrates.

Description

Preparation method of SbOCl material based on ALD technology
Technical Field
The invention relates to a preparation method of an SbOCl material based on an ALD (atomic layer deposition) technology, belonging to the field of nano materials.
Background
The photocatalytic technology converts the green and abundant solar energy into chemical energy which is convenient to be directly utilized, and is considered to be one of the most potential green means for solving the problems of energy shortage and environmental pollution. The photocatalyst generates holes and electrons with oxidation-reduction capability under illumination to drive the breaking and generation of chemical bonds, has potential application in the fields of pollutant degradation, water decomposition for hydrogen production, carbon dioxide reduction and the like, and is widely concerned by researchers all over the world. Therefore, the development of new and highly efficient photocatalytic materials is one of the key directions in photocatalytic technology.
It is well known in the art that the properties of a material depend on its structure, which is limited by the method of its preparation. Up to now, SbOCl has been used only as a flame retardant due to its excellent flame retardant synergy, and its synthesis method mainly includes an acid synthesis method and the like.
ALD technology is a method of forming target materials by alternately pulsing vapor phase precursors into a reaction chamber and chemically reacting on the deposition substrate, with self-limiting and self-saturating features. ALD has excellent reproducibility and enables precise control of material loading, material composition and atomic active site distribution.
Based on the background, the invention provides a preparation method of an SbOCl material based on an ALD technology, and the obtained SbOCl material can be applied to the field of photocatalysis.
Disclosure of Invention
In order to achieve the above object, the present invention provides a method for preparing SbOCl material based on ALD technology, comprising the following steps:
alternately leading the vaporized Sb source SbCl to be in vacuum3Introducing oxygen source water into a reaction cavity of Atomic Layer Deposition (ALD) equipment placed in advance into a substrate in a pulse mode, wherein the alternating pulse mode is as follows: SbCl3Pulse t1→ cleaning t2Pulse of water t →3→ cleaning t4Completing a single growth cycle in this mode; and repeating a plurality of single growth cycles at a specific deposition temperature to obtain the sediment with the SbOCl material.
Preferably, the vaporized Sb source SbCl is introduced into the reaction chamber in a pulse mode3Of the single pulse of (a) duration t1Is 0.5 to 20 seconds.
Preferably, vaporized SbCl3And introducing the carrier gas in a pulse mode in the presence of the carrier gas, wherein the flow rate of the carrier gas is 50-200 sccm.
Preferably, the duration t of a single pulse of vaporized oxygen source water is pulsed into the reaction chamber3Is 1-10 s.
Preferably, the gasified water is introduced in a pulse mode in the presence of a carrier gas, and the flow rate of the carrier gas is 10-200 sccm.
Preferably, the cleaning time t2、t4Is 20 to 50 seconds.
Preferably, the purging refers to purging with high-purity nitrogen or high-purity argon.
Preferably, the deposition temperature is 30-300 ℃.
Preferably, the single cycle of operation is repeated for 1-2000 times, and the SbOCl materials with different thicknesses or loading amounts are prepared by repeating the operation for different times.
Preferably, the carrier gas is high-purity nitrogen or high-purity argon, and the purity is more than or equal to 99.999%.
Preferably, the substrate comprises graphene, titanium oxide, silicon dioxide, silicon, C3N4One or more of cadmium sulfide, strontium titanate and cerium oxide.
The invention also provides the SbOCl material prepared by the method.
Finally, the invention provides the use of the above-described method or of SbOCl materials in the field of photocatalysis.
Preferably, the application comprises photocatalytic degradation of organic contaminants.
Compared with the prior art, the invention has the following advantages:
(1) the method adopts the atomic layer deposition technology to prepare the SbOCl material, and can realize accurate control on material load, material components and atomic active site distribution.
(2) Compared with the prior art, the SbOCl prepared by the method has better photocatalytic performance under the condition of the same or lower load.
(3) The method can be used for various substrates such as graphene, titanium oxide, silicon dioxide, silicon and C3N4Cadmium sulfide, strontium titanate, cerium oxide, and the like exhibit excellent compatibility.
Drawings
Fig. 1 is a TEM image of SbOCl nanomaterial of this example 1.
Detailed Description
The invention provides a method for growing a SbOCl-containing material by an atomic layer deposition technology, which comprises the following steps: alternately leading the vaporized Sb source SbCl to be in vacuum3Introducing oxygen source water into a reaction cavity of Atomic Layer Deposition (ALD) equipment placed in advance into a substrate in a pulse mode, wherein the alternating pulse mode is as follows: SbCl3Pulse t1→ cleaning t2Pulse of water t →3→ cleaning t4Completing a single growth cycle in this mode; and repeating a plurality of single growth cycles at a specific deposition temperature to obtain the sediment with the SbOCl material.
And putting the substrate into a wafer transferring cavity of the atomic layer deposition equipment, vacuumizing to realize a vacuum environment required by deposition, and transferring the substrate into the reaction cavity after reaching the required vacuum degree so as to prevent the water and oxygen in the air from diffusing to the reaction cavity to influence the growth of the material. In order to further ensure that no residual water oxygen exists in each pipeline and the cavity of the atomic layer deposition equipment, before the substrate is placed, the pipeline and the reaction cavity of the atomic layer deposition equipment are preferably subjected to evacuation treatment.
The Sb source is heated and gasified to obtain the gas-phase Sb source, the heating temperature of the Sb source is preferably 30-90 ℃, more preferably 40-80 ℃, and most preferably 45-60 ℃, and specifically, in the embodiment of the invention, the heating temperature can be 45 ℃, 50 ℃, 55 ℃ or 60 ℃.
In the present invention, the duration t of a single pulse of the gas-phase Sb source1Preferably 0.5-20 s, more preferably 1-15 s, and most preferably 4-8 s; specifically, in the embodiment of the present invention, it may be 4s, 6s, 7s, or 8 s.
In the present invention, the deposition temperature is preferably 30 to 300 ℃, more preferably 50 to 250 ℃, and most preferably 100 to 160 ℃, specifically, in the embodiment of the present invention, 100 ℃, 120 ℃, 140 ℃ or 160 ℃.
In the present invention, the carrier gas of the gas phase Sb source is preferably high-purity nitrogen or high-purity argon, and the flow rate of the carrier gas is preferably 50 to 200sccm, more preferably 60 to 150sccm, and most preferably 100 to 120sccm, and specifically may be 100sccm, 105sccm, 110sccm, or 120 sccm.
In the invention, after the deposition of the Sb source is finished for one time, the reaction cavity is preferably cleaned by adopting high-purity nitrogen or high-purity argon for cleaning time t2Preferably 20 to 50s, more preferably 25 to 45s, and most preferably 30 to 40 s.
In the present invention, it is preferable that the oxygen source water is heated and vaporized to form a gaseous oxygen source. The temperature of the heated carbon source is preferably 30 to 120 ℃, more preferably 35 to 75 ℃, and most preferably 45 to 60 ℃, specifically, in the embodiment of the invention, the temperature may be 45 ℃, 50 ℃, 55 ℃ or 60 ℃.
In the invention, the duration of the single pulse of the oxygen source water is preferably 1-10 s, more preferably 1-8 s, and most preferably 2-5 s, and specifically, in the embodiment of the invention, the duration may be 2s, 3s, 4s, or 5 s.
In the present invention, the carrier gas of the oxygen source water is preferably high-purity nitrogen or high-purity argon, and the flow rate of the carrier gas is preferably 10 to 200sccm, and specifically may be 20sccm, 120sccm, 150sccm, or 200 sccm.
In the invention, after the primary reduction is completed, the reaction cavity is preferably cleaned by adopting high-purity nitrogen or high-purity argon for cleaning time t4Preferably 20 to 50s, more preferably 25 to 45s, and most preferably 30 to 40 s. .
The invention preferably repeats the above SbCl3Pulse t1→ cleaning t2Pulse of water t →3→ cleaning t4The number of times of the single circulation process and the repeated circulation depends on the actual requirement. In the present invention, the number of cycles is preferably 1 to 2000, more preferably 150 to 1000, and most preferably 200 to 500. Specifically, in the embodiment of the present invention, it may be 200 times, 300 times, 400 times, or 500 times.
In order to further illustrate the present invention, the following will describe in detail a method for preparing SbOCl material based on ALD technique, which is provided by the present invention, with reference to the following examples.
Example 1
With SbCl3Is a Sb source, takes water as an oxygen source, and the preparation method of the SbOCl material based on the ALD technology comprises the following steps:
with TiO2Powder (average particle size of 60nm) as a substrate, placing the substrate in a reaction chamber, depositing at 160 deg.C, and adding SbCl3Heating to 45 deg.C for gasification, introducing gaseous SbCl with high-purity nitrogen as carrier gas3The flow rate of the carrier gas is 100sccm, and the pulse time is 4 s; complete one SbCl3After the pulse, high-purity nitrogen is used for cleaning, and the cleaning time is 30 s; heating oxygen source water to 45 deg.C for gasification, and using high-purity nitrogen as carrier gasIntroducing water into the reaction cavity in a pulse mode with the flow of 20sccm for 2s, and reacting the water with the Sb source deposited on the substrate to obtain the substrate containing the nano SbOCl material; and after one water pulse is finished, cleaning by adopting high-purity nitrogen for 30s, namely finishing one ALD cycle.
The above steps are repeatedly cycled for 500 times to obtain an SbOCl nanomaterial with a certain loading amount, the SbOCl loading amount is 3 wt% by testing, and fig. 1 is a TEM image of the SbOCl nanomaterial prepared in this embodiment.
Further, 50mg of each of the above-mentioned 3 wt% SbOCl/TiO precipitates was taken2With 50mg of pure substrate TiO2As a catalyst, 20g/L of phenol solution (20 mL each) is degraded under 365nm illumination, the two groups of reactions before illumination are magnetically stirred under the same stirring speed for half an hour under dark conditions, an illumination degradation experiment is carried out after dark adsorption, samples are taken every half an hour to carry out phenol concentration test, the degradation rate is calculated, and the photocatalytic performance of the material is evaluated, wherein the degradation rate is (initial phenol concentration-phenol concentration when sampling) or initial phenol concentration.
3 wt% SbOCl/TiO was tested2As a photocatalytic material, phenol can be completely degraded within 1.5 hours (namely the degradation rate is 100 percent), and pure substrate TiO can be used as a substrate2As a catalyst, the degradation rate of phenol is only 76% in 8 hours, and the result shows that the SbOCl material prepared in the embodiment has photocatalytic performance and good performance, and the catalyst prepared in the embodiment still has good phenol degradation effect after being recycled for 5 times (the degradation rate of phenol is higher than 97% in 1.5 hours), and has good durability and stability.
Example 2
With SbCl3Is a Sb source, takes water as an oxygen source, and the preparation method of the SbOCl material based on the ALD technology comprises the following steps:
taking graphene powder (industrial grade) as a substrate, placing the substrate in a reaction chamber, depositing at 120 ℃, and adding SbCl3Heating to 55 deg.C for gasification, introducing gaseous SbCl with high-purity argon as carrier gas3The flow rate of carrier gas is 110sccm, and the pulse time is 6 s; go toTo form an SbCl3Cleaning with high-purity argon after pulse for 34 s; heating oxygen source water to 50 ℃ to gasify the oxygen source water, introducing water into a reaction cavity in a pulse mode by taking high-purity argon as carrier gas with the flow rate of 120sccm and the pulse time of 3s, and reacting the water with an Sb source deposited on a substrate to obtain the substrate containing the nano SbOCl material; and after one water pulse is finished, cleaning by adopting high-purity argon for 35s, namely finishing one ALD cycle.
And (3) repeatedly circulating the steps for 400 times to obtain the SbOCl nano material with a certain load, wherein the SbOCl load is 2.4 wt% through tests.
Phenol was degraded as in example 1, and it was tested that 2.4 wt% SbOCl/graphene photocatalytic material could achieve complete degradation of phenol within 1.6 hours (i.e. degradation rate 100%).
Example 3
With SbCl3Is a Sb source, takes water as an oxygen source, and the preparation method of the SbOCl material based on the ALD technology comprises the following steps:
using strontium titanate as substrate, placing the substrate in a reaction chamber, depositing at 140 deg.C, and adding SbCl3Heating to 50 deg.C for gasification, introducing gaseous SbCl with high-purity nitrogen as carrier gas3The flow rate of carrier gas is 105sccm, and the pulse time is 7 s; complete one SbCl3After the pulse, high-purity nitrogen is used for cleaning, and the cleaning time is 37 s; heating oxygen source water to 60 ℃ to gasify the oxygen source water, introducing water into a reaction cavity in a pulse mode by taking high-purity nitrogen as carrier gas with the flow rate of 150sccm and the pulse time of 4s, and reacting the water with an Sb source deposited on a substrate to obtain the substrate containing the nano SbOCl material; after one water pulse is completed, the system is purged with high purity nitrogen for 38 seconds, i.e., one ALD cycle is completed.
And (3) repeatedly circulating the steps for 300 times to obtain the SbOCl nano material with a certain load, wherein the SbOCl load is 1.8 wt% through tests.
Phenol was degraded as in example 1 and it was tested that phenol could be completely degraded in 1.8 hours with 1.8 wt% SbOCl/strontium titanate photocatalytic material (i.e. degradation rate 100%).
Example 4
With SbCl3Is a Sb source, takes water as an oxygen source, and the preparation method of the SbOCl material based on the ALD technology comprises the following steps:
silicon dioxide is used as a substrate, the substrate is placed in a reaction chamber, the deposition temperature is 100 ℃, and SbCl is added3Heating to 60 deg.C for gasification, introducing gaseous SbCl with high-purity argon as carrier gas3The flow rate of carrier gas is 120sccm, and the pulse time is 8 s; complete one SbCl3Cleaning with high-purity argon after pulse for 40 s; heating oxygen source water to 55 ℃ to gasify the oxygen source water, introducing water into the reaction cavity in a pulse mode by taking high-purity argon as carrier gas with the flow rate of 200sccm and the pulse time of 5s, and reacting the water with an Sb source deposited on the substrate to obtain the substrate containing the nano SbOCl material; and after one water pulse is finished, cleaning by adopting high-purity argon for 40s, namely finishing one ALD cycle.
And (3) repeatedly circulating the steps for 200 times to obtain the SbOCl nano material with a certain load, wherein the SbOCl load is 1.1 wt% through tests.
Phenol was degraded as in example 1 and it was tested that phenol could be completely degraded in less than 2 hours (i.e. 100% degradation) with 1.1 wt% SbOCl/silica photocatalytic material.
Comparative example 1
When Sb [ (CH)3)2N]3As a source of Sb, and water as an oxygen source, a material was prepared according to the method of example 1, comprising the steps of:
with TiO2Powder (grain size 60nm) is used as a substrate, the substrate is placed in a reaction chamber, the deposition temperature is 160 ℃, and Sb [ (CH)3)2N]3Heating to 85 deg.C for gasification, introducing gaseous Sb [ (CH) with high-purity nitrogen as carrier gas3)2N]3The flow rate of the carrier gas is 100sccm, and the pulse time is 4 s; complete an Sb [ (CH)3)2N]3After the pulse, high-purity nitrogen is used for cleaning, and the cleaning time is 30 s; introducing oxygenHeating source water to 45 ℃ to gasify the source water, introducing water into the reaction cavity in a pulse mode by taking high-purity nitrogen as carrier gas with the flow rate of 20sccm and the pulse time of 2 s; and after one water pulse is finished, cleaning by adopting high-purity nitrogen for 30s, namely finishing one ALD cycle.
The steps are repeatedly cycled for 500 times, and no SbOCl material can be obtained through the test.
Comparative example 2
When using SbCl3As a source of Sb, and oxygen as an oxygen source, a material was prepared according to the method of example 1, comprising the steps of:
with TiO2Powder (particle size 60nm) as substrate, placing the substrate in a reaction chamber, depositing at 160 deg.C, and adding SbCl3Heating to 45 deg.C for gasification, introducing gaseous SbCl with high-purity nitrogen as carrier gas3The flow rate of the carrier gas is 100sccm, and the pulse time is 4 s; complete one SbCl3After the pulse, high-purity nitrogen is used for cleaning, and the cleaning time is 30 s; high-purity nitrogen is used as carrier gas, the flow rate of the carrier gas is 20sccm, oxygen is introduced into the reaction cavity in a pulse mode, and the pulse time is 2 s; and after one water pulse is finished, cleaning by adopting high-purity nitrogen for 30s, namely finishing one ALD cycle.
The steps are repeatedly circulated for 500 times to obtain the SbOCl nano material with a certain load, the SbOCl load is only 0.27 wt% through tests, and compared with the SbOCl nano material in the example 1, the deposition amount of the SbOCl is obviously reduced.
Comparative example 3
The acid synthesis method is adopted to prepare SbOCl material: in a three-neck flask, a certain amount of concentrated hydrochloric acid is added firstly, and then a proper amount of Sb is added4O5Cl2(purity 98.5%) and TiO2Powder (particle size 60nm), stirring to make Sb4O5Cl2And (4) dissolving. Dropping concentrated sulfuric acid into concentrated hydrochloric acid to produce HCl gas, washing the HCl gas in a gas cylinder with concentrated sulfuric acid, introducing the HCl gas into the solution for about 1 hr, stopping introducing the HCl gas, and adding Sb4O5Cl2The mixture was heated to 110 ℃ and boiled under reflux for 50 minutes. Filtering the reaction precipitate, washing with ethanol until no chloride ion existsAfter drying at 75 ℃ (or vacuum drying), SbOCl material is obtained, and the SbOCl loading is only 5.3 wt% through testing.
Further, 50mg of 5.3 wt% of SbOCl/TiO obtained by the above deposition were each used2With 50mg of pure substrate TiO2As a catalyst, 20g/L of phenol solution (20 mL) is respectively degraded under 365nm illumination, the two groups of reactions before illumination are magnetically stirred for half an hour under the same stirring speed under the dark condition, an illumination degradation experiment is carried out after dark adsorption, samples are taken every half an hour to carry out phenol concentration test, the degradation rate is calculated, and the material photocatalysis performance is evaluated.
The 5.3 wt% SbOCl/TiO prepared in this comparative example was tested2As a photocatalytic material, the phenol degradation rate at 1.5 hours is only 57%, and the degradation effect is obviously lower than that in example 1 under the condition of higher SbOCl loading.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (14)

1. A preparation method of an SbOCl material based on an ALD technology is characterized by comprising the following steps:
alternately leading the vaporized Sb source SbCl to be in vacuum3And oxygen source water is introduced into a reaction cavity of the atomic layer deposition ALD device which is placed in the substrate in advance in a pulse mode, and the alternating pulse mode is as follows: SbCl3Pulse t1→ cleaning t2Pulse of water t →3→ cleaning t4Completing a single growth cycle in this mode; repeating a plurality of single growth cycles at a specific deposition temperature to obtain a sediment with SbOCl material;
wherein, the Sb source after gasification is SbCl3Introducing the carrier gas in a pulse mode in the presence of a carrier gas, wherein the flow rate of the carrier gas is 50-200 sccm; and introducing the gasified oxygen source water in a pulse mode in the presence of a carrier gas, wherein the flow rate of the carrier gas is 10-200 sccm.
2. The method for preparing SbOCl material based on ALD technology as claimed in claim 1, wherein SbCl is3Time of pulse t1Is 0.5 to 20 seconds.
3. A method for preparing SbOCl material based on ALD technology as claimed in claim 1 or 2, characterized in that the pulse time t of water31 to 10s, and a cleaning time t2、t4Is 2 to 50 seconds.
4. The method for preparing SbOCl material based on ALD technology of claim 1 or 2, wherein a single growth cycle is repeated 1-2000 times.
5. The method for preparing SbOCl material based on ALD technology as claimed in claim 3, characterized in that a single growth cycle is repeated 1-2000 times.
6. The method for preparing SbOCl material based on ALD technology as claimed in any one of claims 1 to 2 or 5, wherein the deposition temperature is 30 to 300%oC。
7. The preparation method of SbOCl material based on ALD technology as claimed in claim 3, wherein the deposition temperature is 30-300%oC。
8. The preparation method of SbOCl material based on ALD technology as claimed in claim 4, wherein the deposition temperature is 30-300%oC。
9. The method for preparing SbOCl material based on ALD technology of any one of claims 1-2, 5 or 7-8, wherein the substrate comprises graphene, titanium oxide, silicon dioxide, silicon, C3N4One or more of cadmium sulfide, strontium titanate and cerium oxide.
10. The method for preparing SbOCl material based on ALD technology as claimed in claim 3, wherein the substrate comprises graphene, titanium oxide, silicon dioxide, silicon, C3N4One or more of cadmium sulfide, strontium titanate and cerium oxide.
11. The method for preparing SbOCl material based on ALD technology as claimed in claim 4, wherein the substrate comprises graphene, titanium oxide, silicon dioxide, silicon, C3N4One or more of cadmium sulfide, strontium titanate and cerium oxide.
12. The method for preparing SbOCl material based on ALD technology of claim 6, wherein the substrate comprises graphene, titanium oxide, silicon dioxide, silicon, C3N4One or more of cadmium sulfide, strontium titanate and cerium oxide.
13. The preparation method of the SbOCl material based on the ALD technology as claimed in any one of claims 1 to 12.
14. The preparation method of the SbOCl material based on the ALD technology as claimed in any one of claims 1 to 12 or the application of the SbOCl material in the photocatalysis field as claimed in claim 13.
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