CN115709086A - Purple phosphorus-based photocatalytic material and preparation method and application thereof - Google Patents
Purple phosphorus-based photocatalytic material and preparation method and application thereof Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 119
- 239000011574 phosphorus Substances 0.000 title claims abstract description 118
- 239000000463 material Substances 0.000 title claims abstract description 106
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002086 nanomaterial Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000523 sample Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 239000004570 mortar (masonry) Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 claims description 2
- 150000003346 selenoethers Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000001338 self-assembly Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000010453 quartz Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
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- 239000000376 reactant Substances 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
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- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 239000000498 cooling water Substances 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a purple phosphorus-based photocatalytic material and a preparation method and application thereof, wherein the method comprises the following steps: dispersing the purple phosphorus nano material and the two-dimensional material in an organic solvent, performing ultrasonic treatment, performing suction filtration, washing and drying to obtain the purple phosphorus-based photocatalytic material. The purple phosphorus is constructed into the 2D/2D composite material, and the material composition is the first creation; purple phosphorus and other two-dimensional materials can form a compact composite structure through mutual attraction self-assembly under the solvent ultrasonic auxiliary condition, so that the prepared photocatalytic material has better catalytic activity and higher stability.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a purple phosphorus-based photocatalytic material and a preparation method and application thereof.
Background
Hydrogen (H) 2 ) The combustion heat value is high, and combustion products are free of pollution, so that the fuel is the first choice of clean energy in the future. Recently, research and development of high-efficiency hydrogen production technology has been conductedHas been paid high attention to all countries in the world, and particularly utilizes solar energy to decompose aquatic product H at room temperature by photocatalysis technology 2 And is a research hotspot focused by scientists in the global energy field. In a photocatalytic reaction system, the reasonable design of a catalytic material is the key for realizing high-efficiency photolysis of water to produce hydrogen.
At present, inorganic semiconductor photocatalysts based on ultraviolet response are widely researched; however, less than 5% of solar energy exists in the ultraviolet spectrum. Therefore, in the design of the 2D/2D van der Waals heterojunction photocatalyst, the 2D narrow-band semiconductor material with the searched broad spectral response can further utilize solar energy resources, and realize multi-strategy synergistic effect on the basis of high-efficiency charge separation, so that the photocatalytic conversion efficiency is improved.
Recently, two-dimensional alkene materials represented by Black Phosphorus (BP) are high-efficiency photocatalytic materials with wide spectrum absorption due to excellent performances such as a layered structure, adjustable band gap (0.3-2.0 eV) and the like, and are widely applied to the field of 2D/2D van der waals heterojunction photocatalysis. However, the limited stability of BP-based materials in photocatalytic systems limits their wider use, mainly due to O 2 The reaction with the lone pair of electrons vertical to the BP surface destroys the layered structure and loses the catalytic activity.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a purple phosphorus-based photocatalytic material, a preparation method and an application thereof, and aims to solve the problem of poor stability of the existing black phosphorus-based photocatalytic material.
A preparation method of a purple phosphorus-based photocatalytic material comprises the following steps:
dispersing the purple phosphorus nano material and the two-dimensional material in an organic solvent, performing ultrasonic treatment, performing suction filtration, washing, drying, and drying to obtain the purple phosphorus-based photocatalytic material.
Optionally, the preparation method of the purple phosphorus-based photocatalytic material, wherein the preparation of the purple phosphorus nanomaterial comprises:
putting the purple phosphorus block into a mortar for grinding to obtain purple phosphorus powder;
and transferring the purple phosphorus powder into ultrasonic equipment by using the organic solvent, carrying out ultrasonic treatment by using a probe, and carrying out centrifugal screening to obtain the purple phosphorus nano material.
Optionally, the preparation method of the purple phosphorus-based photocatalytic material is characterized in that the two-dimensional material is selected from black phosphorus and g-C 3 N 4 One or more of graphene, two-dimensional sulfide, two-dimensional selenide, two-dimensional oxynitride and a two-dimensional metal organic framework material.
Optionally, the preparation method of the purple phosphorus-based photocatalytic material comprises the step of selecting the organic solvent from one or more of N-methylpyrrolidone, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, isopropanol, sec-butyl alcohol, isopropylamine, methanol, ethanol and isopropanol.
Optionally, the preparation method of the purple phosphorus-based photocatalytic material, wherein the molar ratio of the purple phosphorus nano material to the two-dimensional material is 0.01:1 to 100:1.
optionally, the purple phosphorus-based photocatalytic material is prepared by a method, wherein the purple phosphorus nano material has a size of 1nm to 5 μm and a thickness of 0.5 to 500nm.
Optionally, the preparation method of the purple phosphorus-based photocatalytic material, wherein the step of grinding the purple phosphorus block in a mortar to obtain the purple phosphorus powder specifically comprises:
putting the purple phosphorus block into a mortar, adding a certain amount of the organic solvent, and grinding to obtain purple phosphorus powder; wherein the mass ratio of the purple phosphorus block to the organic solvent is 0.1:1 to 1:50.
optionally, the preparation method of the purple phosphorus-based photocatalytic material comprises the step of performing ultrasonic treatment on the probe, wherein the ultrasonic power of the probe is 5W-100W, and the ultrasonic time is 0.1-10 h.
The purple phosphorus-based photocatalytic material is prepared by the preparation method.
The purple phosphorus-based photocatalytic material is applied to photocatalytic decomposition of water to prepare hydrogen.
Has the advantages that: compared with the prior art, the purple phosphorus is constructed into the 2D/2D composite material, and the material composition is the first creation; purple phosphorus and other two-dimensional materials can form a compact composite structure through mutual attraction self-assembly under the solvent ultrasonic auxiliary condition, so that the prepared photocatalytic material has better catalytic activity and higher stability.
Drawings
Fig. 1 is a schematic diagram of the synthesis of a purple phosphorus-based photocatalytic material provided by an embodiment of the present invention;
fig. 2 is a scanning electron microscope image of the purple phosphorus-based photocatalytic material provided by the embodiment of the invention;
fig. 3 is a Tauc spectrum of the purple phosphorus-based photocatalytic material provided by the embodiment of the present invention (used for calculating the forbidden bandwidth of the material and determining the photoresponse capability of the material);
fig. 4 is a full spectrum diagram of X-ray photoelectron spectrum of the purple phosphorus-based photocatalytic material provided by the embodiment of the present invention (which can show that the surface of the material has three elements of C, N, and P at the same time, meaning that there is better mutual contact);
fig. 5 shows the area integral differential charge density of the purple phosphorus-based photocatalytic material provided by the embodiment of the present invention (above 0 represents positive charge accumulation, the lower part represents negative charge accumulation, and a large amount of positive and negative charges are accumulated at the interface, which has strong interaction).
Detailed Description
The invention provides a purple phosphorus-based photocatalytic material and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
(1) Synthesis of lumpy purple phosphorus
470mg of red phosphorus (Allatin, 99.999%) was uniformly mixed with 10mg of tin (Alfa Aesar, 99.995%) and 18mg of tin iodide (Alfa Aesar, 99.998%), and the mixture was sealed in a 14 cm-long quartz tube (inner diameter 10 mm, thickness 2 mm) with 10 mm inside -4 Vacuum is applied. The quartz tube was then placed horizontally at one end of a tube furnace (OTF-1200X-III).
The temperature of the end of the tube furnace where the quartz tube is not placed is kept at 450 ℃, the temperature is kept for 6 hours, and the temperature of the reactant is kept at room temperature to prevent the reactant from transferring back. The quartz tube is divided into two regions, one region is provided with reactant red phosphorus, and the other region is provided with a product recovery region (referred to as a vacant region). First, the quartz tube was heated for 8 hours while raising the temperature of one end of the reactant to 650 ℃ and the vacant area to 530 ℃ and kept at this condition for 5 hours. Then, the two zones of the quartz tube were cooled to 550 ℃ and 630 ℃ over a period of 10 hours, respectively, and held for 30 hours. Finally, the temperature of different areas in the quartz tube is reduced to room temperature, which takes 100 hours. And (3) washing and cleaning unreacted raw materials, and recovering the synthesized purple phosphorus for further use, wherein the yield of the purple phosphorus is 36%.
(2) Size control of purple phosphorus nano material
Referring to fig. 1, a proper mass of purple phosphorus block (200 mg) was weighed, placed in an agate mortar, and 2-3 drops of N-methylpyrrolidone (NMP) solvent were added dropwise to improve the lubricity of the material during grinding. The milling time was 20 minutes. Then, the ground purple phosphorus material was transferred to an ultrasonic container with NMP, and further peeled by probe ultrasonic. The ultrasonic time is 1 hour, the power is 20w, and a cold well at 5 ℃ is arranged outside the container, so that the influence of overhigh temperature on the material is prevented. The ultrasound was operated with a program of 8 seconds on and 2 seconds off. And finally, screening and separating the purple phosphorus material subjected to ultrasonic treatment by a centrifugation method, and respectively centrifuging for 20 minutes under the condition of 500 revolutions per minute to obtain the purple phosphorus nano material with the size of 200-500nm of sheet diameter and 200-800 layers. The purple phosphorus nano material is cleaned by ethanol and ultrapure water, dried in vacuum overnight and recovered for later use.
Example 2
(1) The synthesis of lumpy purple phosphorus was carried out as described in example 1.
(2) Size control of purple phosphorus nano material
The purple phosphorus block (200 mg) with proper mass is weighed and put into an agate mortar, and 2-3 drops of N-methylpyrrolidone (NMP) solvent are dropped to improve the lubricity of the material in the grinding process. The milling time was 20 minutes. Then, the ground purple phosphorus material was transferred to an ultrasonic container with NMP, and further peeled by probe ultrasonic. The ultrasonic time is 1 hour, the power is 40w, and a cold well with the temperature of 5 ℃ is arranged outside the container, so that the influence of overhigh temperature on the material is prevented. The ultrasound was operated with a program of 8 seconds on and 2 seconds off. And finally, screening and separating the ultraviolet phosphor material subjected to ultrasonic treatment by a centrifugation method, and respectively centrifuging for 20 minutes under the condition of 1000 revolutions per minute to obtain the ultraviolet phosphor nano material with the size of 100-200nm and the number of layers of 50-200. The purple phosphorus nano material is cleaned by ethanol and ultrapure water, dried in vacuum overnight and recovered for later use.
Example 3
(1) The synthesis of lumpy purple phosphorus was carried out as described in example 1.
(2) Size control of purple phosphorus nano material
The purple phosphorus block (200 mg) with proper mass is weighed and put into an agate mortar, and 2-3 drops of N-methylpyrrolidone (NMP) solvent are dropped to improve the lubricity of the material in the grinding process. The milling time was 20 minutes. Then, the ground purple phosphorus material was transferred to an ultrasonic container with NMP, and further peeled by probe ultrasonic. The ultrasonic time is 1 hour, the power is 60w, and a cold well at 5 ℃ is arranged outside the container, so that the influence of overhigh temperature on the material is prevented. The ultrasound was operated with a program of 8 seconds on and 2 seconds off. And finally, screening and separating the ultraviolet phosphor material subjected to ultrasonic treatment by a centrifugation method, and respectively centrifuging for 20 minutes under the condition of 2000 revolutions per minute to obtain the ultraviolet phosphor nano material with the size of 50-100nm and the number of layers of 10-50. The purple phosphorus nano material is cleaned by ethanol and ultrapure water, dried in vacuum overnight and recovered for later use.
Example 4
(1) The synthesis of the lumpy purple phosphorus was carried out as described in example 1.
(2) Size control of purple phosphorus nano material
The purple phosphorus block (200 mg) with proper mass is weighed and put into an agate mortar, and 2-3 drops of N-methylpyrrolidone (NMP) solvent are dropped to improve the lubricity of the material in the grinding process. The milling time was 20 minutes. Then, the ground purple phosphorus material was transferred to an ultrasonic container with NMP, and further peeled by probe ultrasonic. The ultrasonic time is 1 hour, the power is 80w, and a cold well at 5 ℃ is arranged outside the container, so that the influence of overhigh temperature on the material is prevented. The ultrasound was operated with a program of 8 seconds on and 2 seconds off. And finally, screening and separating the ultraviolet phosphor material subjected to ultrasonic treatment by a centrifugal method, and respectively centrifuging for 20 minutes under the condition of 5000 r/min to obtain the ultraviolet phosphor nano material with the size of 10-50nm and the number of layers of 5-10. The purple phosphorus nano material is cleaned by ethanol and ultrapure water, and then is recovered for standby after vacuum drying overnight.
Example 5
(1) The synthesis of lumpy purple phosphorus was carried out as described in example 1.
(2) Size regulation of purple phosphorus nano material
The purple phosphorus block (200 mg) with proper mass is weighed and put into an agate mortar, and 2-3 drops of N-methylpyrrolidone (NMP) solvent are dropped to improve the lubricity of the material in the grinding process. The milling time was 20 minutes. Then, the ground purple phosphorus material was transferred to an ultrasonic container with NMP, and further peeled by probe ultrasonic. The ultrasonic time is 1 hour, the power is 100w, and a cold well at 5 ℃ is arranged outside the container, so that the influence of overhigh temperature on the material is prevented. The ultrasound was operated with a program of 8 seconds on and 2 seconds off. And finally, screening and separating the ultrasonically-treated purple phosphorus material by a centrifugation method, and respectively centrifuging the ultrasonically-treated purple phosphorus material for 20 minutes under the condition of 10000 revolutions per minute to obtain the purple phosphorus nano material with the size of 2-10nm and the number of layers of 1-5. The purple phosphorus nano material is cleaned by ethanol and ultrapure water, dried in vacuum overnight and recovered for later use.
Example 6
The preparation process of the purple phosphorus-based composite photocatalytic material is shown in figure 1.
10mg of the purple phosphorus nanomaterial prepared in example 5 above, 20mg of g-C 3 N 4 Then they were simultaneously placed in about 50 ml of NMP for ultrasonic dispersion, the reaction conditions were set to 4 hours, 6 seconds on, 4 seconds off, and a 5 ℃ cold well was on the outside. The mixture was then suction filtered, washed, dried under vacuum overnight and recoveredTo obtain VP/g-C 3 N 4 The catalytic material, the projection electron micrograph of which is shown in fig. 2, can see 0.64nm of lattice fringes, which are attributed to VP, and the following amorphous layered structure is CN. This figure can show that there is good contact between the two while also retaining the original form of the components intact.
As shown in fig. 3, fig. 3 is a Tauc spectrum of the VP, CN and VP/CN composite material, and the numerical value of the forbidden bandwidth of the material can be obtained by calculating the tangent, which indicates the response capability of the material to light. Particularly, after VP is compounded with CN, the photoresponse capability of the material is obviously changed.
As shown in FIG. 4, FIG. 4 is a full graph of X-ray photoelectron spectrum of VP, CN and VP/CN composite material, and it can be seen that the compositions of surface elements of different materials, especially, after the composition, the VP/CN surface has peaks of N1s and P2P at the same time, which shows that the two are well combined together. Moreover, after calibration of the C1s peak, it can be seen that the peak contrast VP of N1s and P2P of VP/CN has a shift, indicating that there is a strong interaction between them, which is one of the bases and reasons for the superior performance of the material.
As shown in FIG. 5, FIG. 5 is a general density function of the VP and CN composite material, and it can be seen that vacuum levels of VP and CN respectively, electronegativity of the material, positive charge of VP at the interface, positive charge of CN at the interface, strong interaction at the joint of the VP and CN, and through analog calculation and the principle of Fermi level matching after the composite material is contacted, charges can be transferred from CN to VP, so that efficient separation and utilization of photo-generated charges are realized.
Example 7
Preparation of purple phosphorus-based composite photocatalytic material
10mg of the purple phosphorus nanomaterial prepared in example 6 and 20mg of graphene are weighed and then placed into about 50 ml of NMP for ultrasonic dispersion, the reaction conditions are set to 4 hours, the operation lasts for 6 seconds, the operation procedure is suspended for 4 seconds, and a cold well at 5 ℃ is arranged outside. Then, the mixture was suction-filtered, washed, and recovered after vacuum drying overnight to prepare for evaluation of photocatalytic performance.
Example 8
Preparation of purple phosphorus-based composite photocatalytic material
10mg of the purple phosphorus nanomaterial prepared in example 6 and 20mg of cadmium sulfide were weighed and then placed in about 50 ml of NMP simultaneously for ultrasonic dispersion, the reaction conditions were set to 4 hours, 6 seconds of operation, 4 seconds of operation pause, and a 5 ℃ cold well was placed outside. Then, the mixture was suction-filtered, washed, and recovered after vacuum drying overnight to prepare for evaluation of photocatalytic performance.
Example 9
Preparation of purple phosphorus-based composite photocatalytic material
10mg of the purple phosphorus nanomaterial prepared in example 6 and 20mg of molybdenum disulfide were weighed and then simultaneously placed in about 50 ml of NMP for ultrasonic dispersion, the reaction conditions were set to 4 hours, 6 seconds of operation, 4 seconds of operation pause, and a cold well at 5 ℃ was arranged outside. Then, the mixture was suction-filtered, washed, and recovered after vacuum drying overnight to prepare for evaluation of photocatalytic performance.
Example 10
Preparation of purple phosphorus-based composite photocatalytic material
10mg of the purple phosphorus nanomaterial prepared in example 6 and 20mg of black phosphorus were weighed and then placed in about 50 ml of NMP simultaneously for ultrasonic dispersion, the reaction conditions were set to 4 hours, 6 seconds of operation, 4 seconds of operation pause, and a 5 ℃ cold well was placed outside. Then, the mixture was suction-filtered, washed, and recovered after vacuum drying overnight to prepare for evaluation of photocatalytic performance.
Example 11
Preparation of purple phosphorus-based composite photocatalytic material
10mg of the purple phosphorus nanomaterial prepared in example 6 and 20mg of boron nitride were weighed and then simultaneously placed in about 50 ml of NMP for ultrasonic dispersion, the reaction conditions were set to 4 hours, 6 seconds of operation, 4 seconds of operation pause, and a cold well at 5 ℃ outside. Then, the mixture was suction-filtered, washed, and recovered after vacuum drying overnight to prepare for evaluation of photocatalytic performance.
The water decomposition performance of the VP material and the purple phosphorus-based composite photocatalytic material prepared in the above examples was analyzed.
The photocatalytic reaction is evaluated by Pofely Labsolar-A6 online photocatalytic reaction equipment, a light source is a 300W Pofely PLS-SXE300D xenon lamp, and the reaction is carried out by a top irradiation method. The reactor was a 200 ml glass vessel sealed with quartz glass.
The specific photocatalytic test steps are as follows: 50mg of the sample was weighed and dispersed in 120ml of 20% by volume aqueous methanol solution, and then the reactor was sealed by applying vacuum grease and then connected to the reaction system. The system was evacuated and prepared to begin the photocatalytic test without a change in pressure within 5 minutes. During the reaction, the reactant solution was kept at about 10 ℃ using a cooling water system. With the system set up, the product composition in the reactor was analyzed every 30 minutes, and the test apparatus was Fuli 9790II gas chromatography (equipped with molecular sieves)
Column and thermal conductivity detector, argon as carrier gas) to analyze the gas products.
The results of the photocatalytic experiments are shown in the following table:
TABLE 1 construction of composite photocatalytic activities by VP in different layers
TABLE 2 different ratios of VP/g-C 3 N 4 (VP is selected from purple phosphorus nanometer material with sheet diameter of 10-50nm and layer number of 5-10, and the material in the table is compounded)
TABLE 3VP and different two-dimensional materials (VP is selected from purple phosphorus nanometer material with diameter of 10-50nm and number of layers of 5-10)
From the above experimental results, it can be seen that the catalyst obtained by compounding the purple phosphorus nanomaterial with the two-dimensional material has activity on hydrogen evolution and CO evolution 2 The reduction activity is obviously improved.
In summary, the invention provides a purple phosphorus-based photocatalytic material and a preparation method and application thereof, wherein the method comprises the following steps: dispersing the purple phosphorus nano material and the two-dimensional material in an organic solvent, performing ultrasonic treatment, performing suction filtration, washing, drying, and drying to obtain the purple phosphorus-based photocatalytic material. The purple phosphorus is constructed into the 2D/2D composite material, and the material composition is the first creation; purple phosphorus and other two-dimensional materials can form a compact composite structure through mutual attraction self-assembly under the solvent ultrasonic auxiliary condition, so that the prepared photocatalytic material has better catalytic activity and higher stability.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a purple phosphorus-based photocatalytic material is characterized by comprising the following steps:
dispersing the purple phosphorus nano material and the two-dimensional material in an organic solvent, performing ultrasonic treatment, performing suction filtration, washing and drying to obtain the purple phosphorus-based photocatalytic material.
2. The method for preparing a purple phosphorus-based photocatalytic material according to claim 1, wherein the method for preparing a purple phosphorus nanomaterial comprises:
putting the purple phosphorus block into a mortar for grinding to obtain purple phosphorus powder;
and transferring the purple phosphorus powder into ultrasonic equipment by using the organic solvent, carrying out ultrasonic treatment by using a probe, and carrying out centrifugal screening to obtain the purple phosphorus nano material.
3. The method for preparing a purple phosphorus-based photocatalytic material according to claim 1, wherein the two-dimensional material is selected from black phosphorus, g-C 3 N 4 One or more of graphene, two-dimensional sulfide, two-dimensional selenide, two-dimensional oxynitride and a two-dimensional metal organic framework material.
4. The method for preparing a purple phosphorus-based photocatalytic material according to claim 1, wherein the organic solvent is one or more selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, isopropyl alcohol, sec-butyl alcohol, isopropyl amine, methanol, ethanol, and isopropyl alcohol.
5. The method for preparing a purple phosphorus-based photocatalytic material according to claim 1, wherein the molar ratio of the purple phosphorus nanomaterial to the two-dimensional material is 0.01:1 to 100:1.
6. the method for preparing a purple phosphorus-based photocatalytic material according to claim 1, wherein the purple phosphorus nanomaterial has a size of 1nm to 5 μm and a thickness of 0.5 to 500nm.
7. The method for preparing a purple phosphorus-based photocatalytic material according to claim 2, wherein the step of grinding the purple phosphorus block in a mortar to obtain a purple phosphorus powder comprises:
putting the purple phosphorus block into a mortar, adding a certain amount of the organic solvent, and grinding to obtain purple phosphorus powder; wherein the mass ratio of the purple phosphorus block to the organic solvent is 0.1:1 to 1:50.
8. the method for preparing the purple phosphorus-based photocatalytic material according to claim 2, wherein the probe is subjected to ultrasonic treatment, wherein the power of the ultrasonic treatment of the probe is 5W to 100W, and the ultrasonic treatment time is 0.1 h to 10h.
9. A purple phosphorus-based photocatalytic material, characterized in that it is produced by the production method according to any one of claims 1 to 8.
10. The use of the purple phosphorus-based photocatalytic material of claim 9 for photocatalytic decomposition of water to produce hydrogen.
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