CN108355696B - Black phosphorus/g-C3N 4 composite visible light photocatalytic material and preparation method and application thereof - Google Patents
Black phosphorus/g-C3N 4 composite visible light photocatalytic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN108355696B CN108355696B CN201810113408.8A CN201810113408A CN108355696B CN 108355696 B CN108355696 B CN 108355696B CN 201810113408 A CN201810113408 A CN 201810113408A CN 108355696 B CN108355696 B CN 108355696B
- Authority
- CN
- China
- Prior art keywords
- black phosphorus
- visible light
- ultrasonic
- preparation
- photocatalytic material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000000463 material Substances 0.000 title claims abstract description 53
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- 238000013329 compounding Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 40
- 239000000523 sample Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 29
- 239000004202 carbamide Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 19
- 239000005457 ice water Substances 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 11
- 229940043267 rhodamine b Drugs 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 230000000593 degrading effect Effects 0.000 abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 8
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 17
- 229910052593 corundum Inorganic materials 0.000 description 14
- 239000010431 corundum Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- -1 black phosphorus alkene Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses black phosphorus/g-C3N4The black phosphorus/g-C is a composite visible light photocatalytic material3N4The composite visible light photocatalytic material is black phosphorus and g-C3N4Ball-milling the composite product, wherein the weight of the black phosphorus is g-C3N40.5-50% by weight. The invention firstly makes visible light response semiconductor black phosphorus and g-C3N4Ball milling and compounding, and effectively improves g-C by constructing a heterostructure3N4So that the prepared black phosphorus/g-C can be used3N4The composite visible light photocatalytic material is used for degrading organic pollutants, is particularly suitable for degrading organic photosensitizers and photoinitiators, such as rhodamine B and the like, and has great application prospect in the field of photocatalytic degradation of organic matters; black phosphorus of the invention/g-C3N4The composite visible light photocatalytic material is prepared by a ball milling method, and the preparation scheme is simple and low in cost.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to black phosphorus/g-C3N4A composite visible light photocatalytic material, a preparation method and application thereof.
Background
With the development of industry, the organic dye waste water is continuously discharged, the total amount and types of the dyes entering the ecological environment are gradually increased, and the ecological pollution caused by the dyes is more and more serious. The dyes in factories are discharged into industrial wastewater in the production process, and can undergo physicochemical reactions such as oxidation, hydrolysis and the like under natural conditions to generate toxic byproducts, thereby greatly harming the living environment of human beings. At present, the traditional pollution treatment means, such as adsorption by a physical method, degradation by a biological method, oxidation reduction by a chemical method and the like, have the defects of high cost, low efficiency and the like, so that the development of an efficient, green and low-cost pollution treatment means is urgent.
TiO has been published since Fujishima et al2After the electrode decomposes water to produce hydrogen under the illumination condition, the photocatalysis technology attracts the attention of scholars in various fields. In which semiconductor materials, e.g. TiO, are used in the field of photodegradation of organic pollutants2Etc. under the excitation of light, photo-generated electrons and holes are generated, and then OH-, O are further generated2 2-The active radicals can participate in oxidation-reduction reaction to mineralize organic pollutants and degrade the organic pollutants into non-toxic organic matter micromolecules or CO2、 H2And O and the like. At present, TiO2The application of the material in the aspect of environmental protection has been reported, but the material is still limited by the defects of low utilization rate of visible light, low quantum efficiency and the like. Therefore, it is necessary to construct and develop a high-efficiency photocatalyst with a broad-spectrum response.
g-C3N4The material is a visible light (absorption edge 450nm, forbidden band width 2.7eV) response semiconductor material with a graphite-like laminated structure, has stable physicochemical properties, simple preparation process and low cost, and is an ideal photocatalytic material. However, the high recombination rate of photogenerated electrons and holes results in g-C3N4The photocatalytic efficiency is poor, so that the g-C is improved3N4The photocatalytic efficiency of (2) is required for g-C3N4And (5) carrying out modification. The construction of the heterojunction by selecting different semiconductors is an effective strategy, and the difference of energy levels is constructed by utilizing the differences of energy band structures of different semiconductors, so that the separation of photoproduction electrons and holes is facilitated, and the catalytic efficiency of the composite photocatalytic material is improved.
The black phosphorus serving as a novel semiconductor material has a graphite-like layered structure, is a direct band gap semiconductor material (the forbidden band width is 0.3eV), and the response of the black phosphorus to light can be expanded to an infrared region; meanwhile, the forbidden bandwidth can be changed by regulating the number of the layers of the black phosphorus alkene. Its unique photochemical properties have attracted much attention.
Disclosure of Invention
The purpose of the invention is to make visible light respond to a semiconductorBlack phosphorus and g-C3N4Compounding, namely preparing the black phosphorus/g-C3N 4 composite visible light photocatalytic material by constructing a heterostructure so as to improve g-C3N4The photocatalytic efficiency of (c).
The technical scheme adopted by the invention is as follows: black phosphorus/g-C3N4The black phosphorus/g-C is a composite visible light photocatalytic material3N4The composite visible light photocatalytic material is black phosphorus and g-C3N4A composite product, the weight of the black phosphorus is g-C3N40.5-50% by weight. Further preferably, the black phosphorus/g-C3N4The composite visible light photocatalytic material is black phosphorus and g-C3N4And ball-milling the compounded product.
Preferably, the weight of the black phosphorus is g-C3N40.5-40% by weight, more preferably, the black phosphorus is present in an amount of g-C3N40.8-30% by weight, more specifically, the black phosphorus is present in g-C3N41% by weight, or the weight of the black phosphorus is g-C3N45% by weight, or the weight of the black phosphorus is g-C3N410% by weight of the total amount of the black phosphorus, or the weight of the black phosphorus is g-C3N430% by weight of the total amount of the black phosphorus, or the weight of the black phosphorus is g-C3N440% by weight.
Preferably, the black phosphorus is ball-milled black phosphorus powder, black phosphorus nanosheets or black phosphorus quantum dots.
Another object of the present invention is to provide a black phosphorus/g-C3N4The preparation method of the composite visible light photocatalytic material comprises the following steps:
1) calcining urea, and grinding to obtain g-C3N4；
2) Dispersing the black phosphorus crystal in an organic solvent, carrying out ultrasonic treatment, separating and drying to obtain black phosphorus powder;
3) mixing black phosphorus powder with g-C3N4Dispersing in polar organic solvent, ultrasonic treating, ball milling, washing and drying to obtain black phosphorus/g-C3N4And compounding the visible light photocatalytic material.
Preferably, in step 1), the calcination is performed in a muffle furnace, and the calcination conditions are controlled as follows: raising the temperature to 450-600 ℃ at the temperature raising rate of 2-10 ℃/min, then preserving the temperature for 60-120min, and then reducing the temperature to the room temperature within 60-120 min.
More preferably, the conditions of the furnace calcination are controlled as follows: raising the temperature to 500-600 ℃ at the temperature rise rate of 5-8 ℃/min, then preserving the temperature for 90-120min, and then reducing the temperature to the room temperature within 90-120 min.
Preferably, in step 2), the organic solvent is selected from N-methylpyrrolidone, and the probe ultrasonic treatment and the ice-water bath ultrasonic treatment are sequentially performed, wherein the conditions of the probe ultrasonic treatment are controlled as follows: the ultrasonic power is 500-1200W, and the ultrasonic time is 2-8 h; the ice-water bath ultrasonic treatment conditions are controlled as follows: the ultrasonic power is 200-500W, and the ultrasonic time is 8-15 h.
More preferably, the conditions of the ultrasonic treatment of the probe are controlled as follows: the ultrasonic power is 800-; the ice-water bath ultrasonic treatment conditions are controlled as follows: the ultrasonic power is 300-500W, and the ultrasonic time is 10-12 h. More specifically, the conditions of the probe ultrasonic treatment are controlled as follows: the ultrasonic power is 1000W, and the ultrasonic time is 3.5 h; the ice-water bath ultrasonic treatment conditions are controlled as follows: the ultrasonic power is 350W, and the ultrasonic time is 10 h.
Preferably, in the step 2), the volume ratio of the mass of the black phosphorus crystals to the organic solvent (N-methylpyrrolidone) is 1g:500-1000 mL; centrifugal separation is adopted, anhydrous ethanol is adopted for centrifugal cleaning in the centrifugal separation process, and the centrifugal rotating speed is 3500-.
More preferably, the ratio of the mass of the black phosphorus crystals to the volume of the N-methylpyrrolidone solvent is 1g:800-1000mL, and still more preferably, the ratio of the mass of the black phosphorus crystals to the volume of the N-methylpyrrolidone solvent is 1g:1000 mL.
In the step 2), the black phosphorus crystal is dispersed in an N-methylpyrrolidone solvent, and probe ultrasound and ice water bath ultrasound treatment are sequentially carried out, so that the black phosphorus crystal can be prepared into black phosphorus powder, namely a thin black phosphorus nanosheet or a black phosphorus quantum dot.
Preferably, in step 3), the polar organic solvent is selected fromFrom lower alcohols, preferably absolute ethanol; g-C3N4The mass ratio of the black phosphorus powder to the black phosphorus powder is 1:0.005-0.5, and the mass of the added ethanol is the black phosphorus powder and g-C3N410-50 times of the total mass of (A). More preferably, g-C3N4The mass ratio of the black phosphorus powder to the black phosphorus powder is 1:0.01-0.1, and the mass of the added ethanol is the black phosphorus powder and g-C3N420-50 times of the total mass of (A).
Preferably, in step 3), the ultrasound is water bath ultrasound, and the conditions of the water bath ultrasound are controlled as follows: the ultrasonic power is 200-500W, and the ultrasonic time is 2-5 min. More preferably, the conditions of the water bath ultrasound are controlled as follows: the ultrasonic power is 350W, and the ultrasonic time is 3 min.
Preferably, in step 3), the conditions of the ball milling treatment are controlled as follows: the rotating speed is 100-. More preferably, the conditions of the ball milling treatment are controlled as follows: the rotating speed is 150-.
More particularly, the invention also provides black phosphorus/g-C3N4The preparation method of the composite visible light photocatalytic material comprises the following steps:
1)g-C3N4the preparation of (1): putting 5-25g of urea into a corundum crucible, putting the corundum crucible into a muffle furnace, heating the corundum crucible to 450-DEG C and 600 ℃ from room temperature at the heating rate of 2-10 ℃/min, then preserving the heat for 60-120min, subsequently cooling the corundum crucible to room temperature within 60-120min, and grinding a sample to obtain g-C3N4；
2) Preparing black phosphorus: grinding the black phosphorus crystal by using a mortar, adding an N-methylpyrrolidone solvent, carrying out probe ultrasonic treatment for 6 hours and ice water bath ultrasonic treatment for 10 hours, then carrying out centrifugal cleaning by using absolute ethyl alcohol, taking the precipitate at the centrifugal speed of 4000r/min, and carrying out vacuum drying. Thus obtaining black phosphorus;
3) black phosphorus/g-C3N4Preparing a composite material: weighing a certain amount of g-C3N4Adding anhydrous ethanol into the materials and prepared black phosphorus powder with different mass, performing water bath ultrasonic treatment for 3min, transferring into a grinding tank, performing ball milling at a rotation speed of 100-300r/min for 3-10h, cleaning the sample with anhydrous ethanol for 3 times, and putting the sample in a vacuum drying oven overnightDrying to obtain black phosphorus/g-C3N4A composite material.
The invention also provides black phosphorus/g-C3N4The composite visible light photocatalytic material is applied to the degradation of organic matters. The black phosphorus/g-C prepared by the invention3N4The composite visible light photocatalytic material has higher photocatalytic efficiency, can be used for visible light photodegradation of organic pollutants, and is particularly suitable for degradation of organic photosensitizers and photoinitiators, such as rhodamine B, aryl imidazole, triarylmethane, onium salts and the like.
The existing photocatalytic pollutant degradation technology has the defect of insufficient utilization rate of visible light or the defect of low separation efficiency of photoproduction electrons and holes. The invention adopts a high-speed ball milling method, in a liquid phase, the two-dimensional black phosphorus nanosheet and the graphite-like layered structure carbon nitride are bonded through Van der Waals force, and finally the black phosphorus/g-C is prepared3N4The composite visible light photocatalytic material can be used for degrading organic pollutants and is beneficial to improving g-C3N4The photocatalysis efficiency of the base material and the application field of the novel semiconductor material black phosphorus are expanded.
The invention has the beneficial effects that: the invention firstly makes visible light response semiconductor black phosphorus and g-C3N4Ball milling and compounding, and effectively improves g-C by constructing a heterostructure3N4So that the prepared black phosphorus/g-C can be used3N4The composite visible light photocatalytic material is used for degrading organic pollutants, is particularly suitable for degrading organic photosensitizers and photoinitiators, such as rhodamine B, aryl imidazole, triarylmethane, onium salts and other organic pollutants, and has great application prospect in the field of photocatalytic degradation of organic matters; black phosphorus of the invention/g-C3N4The composite visible light photocatalytic material is prepared by a ball milling method, and the preparation scheme is simple and low in cost.
Drawings
FIG. 1 shows black phosphorus/g-C prepared in example 13N4XRD pattern of the composite visible light photocatalytic material;
FIG. 2 shows black phosphorus prepared in example 1/g-C3N4A TEM image of the composite visible light photocatalytic material;
FIG. 3 shows black phosphorus/g-C for different black phosphorus loadings3N4And (3) an effect diagram of degrading rhodamine B by using the composite photocatalyst.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications without departing from the principle of the embodiments of the present invention, and these modifications are also considered to be within the scope of the embodiments of the present invention. The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific examples. The embodiments may be modified as appropriate within a range not changing the main claim.
Example 1
Black phosphorus/g-C3N4The preparation method of the composite visible light photocatalytic material comprises the following steps:
1) weighing 10g of urea, placing the urea in a corundum crucible, placing the corundum crucible in a muffle furnace, heating the urea to 550 ℃ from room temperature at the heating rate of 2.2 ℃/min, then preserving the heat for 120min, then cooling the urea to room temperature within 120min, and grinding the urea to obtain the g-C3N4；
2) Weighing 100mg of black phosphorus crystals, grinding the black phosphorus crystals by using a mortar, adding 100mL of N-methylpyrrolidone solvent, carrying out probe ultrasonic treatment and ice-water bath ultrasonic treatment, carrying out centrifugal cleaning by using absolute ethyl alcohol, taking a precipitate at the centrifugal speed of 4000r/min, and carrying out vacuum drying to obtain black phosphorus powder; wherein, the ultrasonic treatment conditions of the probe are controlled as follows: the ultrasonic power is 1000W, and the ultrasonic time is 5 h; the ice-water bath ultrasonic treatment conditions are controlled as follows: the ultrasonic power is 200W, and the ultrasonic time is 15 h;
3) weigh 400mg of g-C3N4Adding 20mL of absolute ethyl alcohol into 20mg of black phosphorus powder, carrying out ultrasonic treatment in a 300W power water bath for 3min, transferring the mixture into a grinding tank, carrying out ball milling for 6h at the rotating speed of 200r/min, finally cleaning a sample by using the absolute ethyl alcohol for 3 times, and drying the sample in a vacuum drying oven at the temperature of 60 ℃ overnight to obtain 5 wt% of black phosphorus/g-C3N4CompoundingA visible light photocatalytic material.
FIG. 1 is 5% wt black phosphorus/g-C prepared in example 13N4XRD pattern of the composite visible light photocatalytic material. The black phosphorus is characterized in that the black phosphorus is positioned in g-C3N4Surface, black phosphorus mass in g-C3N45% by mass.
FIG. 2 shows black phosphorus/g-C prepared in example 13N4And (3) TEM images of the composite visible light photocatalytic material, wherein 2(a) is a low-power transmission electron microscope image, and 2(b) is a high-power transmission electron microscope image. In 2(a), the large pieces and the folds are g-C3N4The black phosphorus can be seen by a high power transmission electron microscope, and the black phosphorus is thinner and uniformly distributed as shown in 2 (b).
Example 2
Black phosphorus/g-C3N4The preparation method of the composite visible light photocatalytic material comprises the following steps:
1) weighing 10g of urea, placing the urea in a corundum crucible, placing the corundum crucible in a muffle furnace, heating the urea to 550 ℃ from room temperature at the heating rate of 2.2 ℃/min, then preserving the heat for 120min, then cooling the urea to room temperature within 120min, and grinding the urea to obtain the g-C3N4；
2) Weighing 100mg of black phosphorus crystal, grinding the black phosphorus crystal by using a mortar, adding 50mL of N-methylpyrrolidone solvent, carrying out probe ultrasonic treatment and ice-water bath ultrasonic treatment, carrying out centrifugal cleaning by using absolute ethyl alcohol, taking a precipitate at the centrifugal speed of 4000r/min, and carrying out vacuum drying to obtain black phosphorus powder; wherein, the ultrasonic treatment conditions of the probe are controlled as follows: the ultrasonic power is 600W, and the ultrasonic time is 6 h; the ice-water bath ultrasonic treatment conditions are controlled as follows: the ultrasonic power is 350W, and the ultrasonic time is 10 h;
3) weighing 400mg of g-C3N4Adding 20mL of absolute ethyl alcohol into 4mg of black phosphorus powder, carrying out ultrasonic treatment in a 250W power water bath for 3min, transferring the mixture into a grinding tank, carrying out ball milling for 6h at the rotating speed of 200r/min, finally cleaning a sample by using the absolute ethyl alcohol for 3 times, and drying the sample in a vacuum drying oven at the temperature of 60 ℃ overnight to obtain 1 wt% of black phosphorus/g-C3N4And compounding the visible light photocatalytic material.
Example 3
Black phosphorus/g-C3N4The preparation method of the composite visible light photocatalytic material comprises the following steps:
1) weighing 10g of urea, placing the urea in a corundum crucible, placing the corundum crucible in a muffle furnace, heating the urea to 550 ℃ from room temperature at the heating rate of 2.2 ℃/min, then preserving the heat for 120min, then cooling the urea to room temperature within 120min, and grinding the urea to obtain the g-C3N4；
2) Weighing 100mg of black phosphorus crystals, grinding the black phosphorus crystals by using a mortar, adding 100mL of N-methylpyrrolidone solvent, performing probe ultrasound and ice-water bath ultrasound, then performing centrifugal cleaning by using absolute ethyl alcohol, taking the precipitate at the centrifugal speed of 4000r/min, and performing vacuum drying to prepare black phosphorus powder; wherein, the ultrasonic treatment conditions of the probe are controlled as follows: the ultrasonic power is 500W, and the ultrasonic time is 7 h; the ice-water bath ultrasonic treatment conditions are controlled as follows: the ultrasonic power is 250W, and the ultrasonic time is 12 h;
3) weighing 400mg of g-C3N4Adding 20mL of absolute ethyl alcohol into 40mg of black phosphorus powder, carrying out ultrasonic treatment in 350W power water bath for 3min, transferring the mixture into a grinding tank, carrying out ball milling for 6h at the rotating speed of 200r/min, finally cleaning a sample by using absolute ethyl alcohol for 3 times, and drying the sample in a vacuum drying oven at the temperature of 60 ℃ overnight to obtain 10 wt% of black phosphorus/g-C3N4And compounding the visible light photocatalytic material.
Example 4
Black phosphorus/g-C3N4The preparation method of the composite visible light photocatalytic material comprises the following steps:
1) weighing 10g of urea, placing the urea in a corundum crucible, placing the corundum crucible in a muffle furnace, heating the urea from room temperature to 600 ℃ at a heating rate of 5 ℃/min, then preserving the heat for 90min, then cooling the urea to room temperature within 90min, and grinding the urea to obtain g-C3N4；
2) Weighing 100mg of black phosphorus crystal, grinding the black phosphorus crystal by using a mortar, adding 80mL of N-methylpyrrolidone solvent, carrying out probe ultrasonic treatment and ice-water bath ultrasonic treatment, carrying out centrifugal cleaning by using absolute ethyl alcohol, taking a precipitate at the centrifugal speed of 3500r/min, and drying in vacuum to obtain black phosphorus powder; wherein, the ultrasonic treatment conditions of the probe are controlled as follows: the ultrasonic power is 1000W, and the ultrasonic time is 3.5 h; the ice-water bath ultrasonic treatment conditions are controlled as follows: the ultrasonic power is 400W, and the ultrasonic time is 15 h;
3) weighing 400mg of g-C3N4Adding 30mL of absolute ethyl alcohol into 120mg of black phosphorus powder, carrying out ultrasonic treatment in 400W power water bath for 5min, transferring the mixture into a grinding tank, carrying out ball milling for 10h at the rotating speed of 100r/min, finally cleaning a sample by using absolute ethyl alcohol for 3 times, and drying the sample in a vacuum drying oven at the temperature of 60 ℃ overnight to obtain 30 wt% of black phosphorus/g-C3N4And compounding the visible light photocatalytic material.
Example 5
Black phosphorus/g-C3N4The preparation method of the composite visible light photocatalytic material comprises the following steps:
1) weighing 10g of urea, placing the urea in a corundum crucible, placing the corundum crucible in a muffle furnace, heating the urea from room temperature to 600 ℃ at the heating rate of 8 ℃/min, then preserving the heat for 100min, then cooling the urea to the room temperature within 100min, and grinding the urea to obtain the g-C3N4；
2) Weighing 200mg of black phosphorus crystal, grinding the black phosphorus crystal by using a mortar, adding 200mL of N-methylpyrrolidone solvent, carrying out probe ultrasound and ice-water bath ultrasound, carrying out centrifugal cleaning by using absolute ethyl alcohol, taking a precipitate at the centrifugal speed of 5000r/min, and drying in vacuum to obtain black phosphorus powder; wherein, the ultrasonic treatment conditions of the probe are controlled as follows: the ultrasonic power is 800W, and the ultrasonic time is 3 h; the ice-water bath ultrasonic treatment conditions are controlled as follows: the ultrasonic power is 500W, and the ultrasonic time is 8 h;
3) weighing 400mg of g-C3N4Adding 30mL of absolute ethyl alcohol into 160mg of black phosphorus powder, carrying out ultrasonic treatment in 500W power water bath for 2min, transferring the mixture into a grinding tank, carrying out ball milling for 8h at the rotating speed of 300r/min, finally cleaning a sample by using absolute ethyl alcohol for 3 times, and drying the sample in a vacuum drying oven at the temperature of 60 ℃ overnight to obtain 40 wt% of black phosphorus/g-C3N4And compounding the visible light photocatalytic material.
Comparative example 1
Black phosphorus/g-C3N4The preparation method of the composite visible light photocatalytic material comprises the following steps:
1) 10g of urea is weighed and placed in a steelPlacing in a muffle furnace, heating to 550 deg.C from room temperature at a rate of 2.2 deg.C/min, maintaining for 120min, cooling to room temperature within 120min, and grinding to obtain g-C3N4；
2) Weighing 400mg of g-C3N4Adding 20mL of absolute ethyl alcohol into the material, carrying out water bath ultrasonic treatment for 3min, transferring the material into a grinding tank, carrying out ball milling for 6h at the rotating speed of 200r/min, finally cleaning the sample by using the absolute ethyl alcohol for 3 times, and putting the sample into a vacuum drying oven at 60 ℃ for overnight drying to obtain 0 wt% of black phosphorus/g-C3N4A composite material.
Application example
Evaluation of black phosphorus/g-C by rhodamine B (RhB) degradation method3N4The visible light photocatalysis performance of the composite visible light photocatalysis material.
The experimental steps are as follows:
weighing black phosphorus/g-C with black phosphorus loading amounts of 0%, 1%, 5% and 10% respectively3N4Composite visible photocatalytic material (corresponding to the products prepared in comparative example 1 and examples 1 to 3) and pure g-C without any treatment3N420mg of catalyst (used as a comparison sample) is respectively added into 20mL of rhodamine B solution (10mg/L), cooling circulating water is started for magnetic stirring, a xenon lamp of 1000W is used as a light source, and ultraviolet light with the wavelength less than 420nm is filtered by an ultraviolet light filter. And before illumination, stirring for 2h under a dark condition to ensure that the photocatalyst surface in the rhodamine B solution reaches adsorption-desorption balance. After the illumination is started, 2mL of the supernatant is taken out every other hour, and after high-speed centrifugation, the supernatant is taken out and the concentration of rhodamine B is tested by an ultraviolet spectrophotometer.
Black phosphorus/g-C of different black phosphorus loading3N4The test result of the composite photocatalyst for degrading rhodamine B is shown in figure 3, and as can be seen from figure 3, the activity of the composite material loaded with black phosphorus for degrading rhodamine B is greatly improved, wherein the composite material with 1% black phosphorus loading shows the highest photodegradation activity.
Claims (6)
1. Black phosphorus/g-C3N4Preparation method of composite visible light photocatalytic materialThe method is characterized by comprising the following steps:
1) calcining urea, and grinding to obtain g-C3N4；
2) Dispersing the black phosphorus crystal in an organic solvent, carrying out ultrasonic treatment, separating and drying to obtain black phosphorus powder;
3) mixing black phosphorus powder with g-C3N4Dispersing in polar organic solvent, ultrasonic treating, ball milling, washing and drying to obtain black phosphorus/g-C3N4Compounding visible light photocatalytic materials;
in the step 3), the ball milling treatment conditions are controlled as follows: the rotating speed is 100-;
the black phosphorus/g-C3N4The composite visible light photocatalytic material is black phosphorus and g-C3N4A composite product, the weight of the black phosphorus is g-C3N40.5-10% by weight.
2. The preparation method according to claim 1, wherein in step 1), the calcination is performed in a muffle furnace, and the calcination conditions are controlled as follows: raising the temperature to 450-600 ℃ at the temperature raising rate of 2-10 ℃/min, then preserving the temperature for 60-120min, and then reducing the temperature to the room temperature within 60-120 min.
3. The preparation method according to claim 1, wherein in the step 2), the organic solvent is selected from N-methylpyrrolidone, and the probe ultrasonic treatment and the ice-water bath ultrasonic treatment are sequentially performed, wherein the conditions of the probe ultrasonic treatment are controlled as follows: the ultrasonic power is 500-1200W, and the ultrasonic time is 2-8 h; the ice-water bath ultrasonic treatment conditions are controlled as follows: the ultrasonic power is 200-500W, and the ultrasonic time is 8-15 h.
4. The preparation method as claimed in claim 1, wherein in the step 2), the volume ratio of the mass of the black phosphorus crystal to the organic solvent is 1g:500-1000 mL; centrifugal separation is adopted, anhydrous ethanol is adopted for centrifugal cleaning in the centrifugal separation process, and the centrifugal rotating speed is 3500-.
5. The method according to claim 1, wherein the polar organic solvent in the step 3) is selected from the group consisting of absolute ethanol, g-C3N4The mass ratio of the black phosphorus powder to the black phosphorus powder is 1:0.01-0.1, and the mass of the added absolute ethyl alcohol is the black phosphorus powder and g-C3N410-50 times of the total mass of (A).
6. The preparation method according to claim 1, wherein in the step 3), the ultrasound is water bath ultrasound, and the conditions of the water bath ultrasound are controlled as follows: the ultrasonic power is 200-500W, and the ultrasonic time is 2-5 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810113408.8A CN108355696B (en) | 2018-02-05 | 2018-02-05 | Black phosphorus/g-C3N 4 composite visible light photocatalytic material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810113408.8A CN108355696B (en) | 2018-02-05 | 2018-02-05 | Black phosphorus/g-C3N 4 composite visible light photocatalytic material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108355696A CN108355696A (en) | 2018-08-03 |
| CN108355696B true CN108355696B (en) | 2021-04-23 |
Family
ID=63004872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810113408.8A Active CN108355696B (en) | 2018-02-05 | 2018-02-05 | Black phosphorus/g-C3N 4 composite visible light photocatalytic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108355696B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109158125B (en) * | 2018-10-15 | 2021-10-26 | 长沙理工大学 | Graphite carbon nitride quantum dot modified zinc oxide catalytic material and preparation method thereof |
| CN109569670B (en) * | 2018-12-05 | 2021-07-16 | 南昌航空大学 | Preparation method of BiOBr/black phosphorus alkene heterojunction nano composite material |
| CN111298815B (en) * | 2018-12-12 | 2021-04-09 | 中国科学院深圳先进技术研究院 | Platinum/phosphorus catalyst and preparation method and application thereof |
| CN109621991A (en) * | 2019-01-21 | 2019-04-16 | 杭州电子科技大学 | A kind of novel solar hydrogen making material and its preparation method and application containing Co-P key |
| CN111318290A (en) * | 2019-01-28 | 2020-06-23 | 南京理工大学 | Application of black phosphorus quantum dots as photosensitizer in photocatalysis |
| CN109772383B (en) * | 2019-03-07 | 2021-12-24 | 华南师范大学 | Sulfur indium zinc/black phosphorus quantum dot and preparation method and application thereof |
| CN110280280B (en) * | 2019-07-31 | 2022-01-28 | 商丘师范学院 | Black phosphorus nanosheet, and preparation method and application of zinc sulfide/black phosphorus nanosheet |
| CN110327952A (en) * | 2019-08-16 | 2019-10-15 | 济南大学 | Self-water absorption type two dimension P/MoS2The preparation method of base composite photocatalyst |
| CN110841670B (en) * | 2019-11-21 | 2021-01-01 | 湖南大学 | Zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst and preparation method thereof |
| CN111167497B (en) * | 2020-01-10 | 2023-01-17 | 苏州科技大学 | Black phosphorus/oxygen-enriched porous graphite phase carbon nitride composite material and preparation method and application thereof |
| CN113522327B (en) * | 2020-04-13 | 2022-09-13 | 深圳先进技术研究院 | Ternary composite photocatalyst, preparation method and application thereof |
| CN111420695A (en) * | 2020-04-22 | 2020-07-17 | 昆明理工大学 | Composite photocatalyst for degrading organic pollutants by visible light and preparation method thereof |
| CN112076769A (en) * | 2020-09-15 | 2020-12-15 | 大连民族大学 | Spherical bismuth vanadate/black phosphorus composite photocatalyst and preparation method thereof |
| CN112717966A (en) * | 2020-12-07 | 2021-04-30 | 上海电力大学 | Two-dimensional black phosphorus-MoO3-xComposite material, preparation method and application thereof |
| CN113385210A (en) * | 2021-06-08 | 2021-09-14 | 太原理工大学 | Photocatalytic hydrogen production catalyst and preparation method and application thereof |
| CN113842939B (en) * | 2021-09-24 | 2023-09-01 | 郑州大学 | Photocatalyst and preparation method thereof |
| CN115709086A (en) * | 2022-11-21 | 2023-02-24 | 深圳先进技术研究院 | Purple phosphorus-based photocatalytic material and preparation method and application thereof |
| CN115739136B (en) * | 2022-12-16 | 2024-02-20 | 中国科学院深圳理工大学(筹) | Black phosphorus purple phosphorus composite material, preparation method thereof, photocatalyst and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200318A (en) * | 2017-06-02 | 2017-09-26 | 国家纳米科学中心 | Two-dimensional material quantum piece and preparation method thereof |
| CN107376967A (en) * | 2017-06-27 | 2017-11-24 | 常州大学 | A kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst |
| CN107469845A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | A kind of black phosphorus/noble metal composite-material, its preparation method and application |
-
2018
- 2018-02-05 CN CN201810113408.8A patent/CN108355696B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200318A (en) * | 2017-06-02 | 2017-09-26 | 国家纳米科学中心 | Two-dimensional material quantum piece and preparation method thereof |
| CN107376967A (en) * | 2017-06-27 | 2017-11-24 | 常州大学 | A kind of preparation method of nitrogenous carbon quantum dot/graphite phase carbon nitride composite photo-catalyst |
| CN107469845A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | A kind of black phosphorus/noble metal composite-material, its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| Black Phosphorus and Polymeric Carbon Nitride Heterostructure for Photoinduced Molecular Oxygen Activation;Yun Zheng，et al.;《Adv. Funct. Mater》;20180108;第1节左栏、第3节、第4节 * |
| Metal-Free Photocatalyst for H2 Evolution in Visible to Near-Infrared Region: Black Phosphorus/Graphitic Carbon Nitride;Mingshan Zhu et al.;《J. Am. Chem. Soc.》;20170831;第139卷;CONCLUSIONS、第13237页右栏 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108355696A (en) | 2018-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108355696B (en) | Black phosphorus/g-C3N 4 composite visible light photocatalytic material and preparation method and application thereof | |
| Fang et al. | Facile synthesis of anatase/rutile TiO2/g-C3N4 multi-heterostructure for efficient photocatalytic overall water splitting | |
| US20200122130A1 (en) | Two-dimensional nitrogen-doped carbon-based titanium dioxide composite material, and preparation method and application thereof for degrading and removing organic pollutants in water | |
| CN111389442B (en) | P-N heterojunction composite material loaded on surface of foamed nickel and preparation method and application thereof | |
| CN111437867B (en) | Composite photocatalyst containing tungsten oxide and preparation method and application thereof | |
| Zhao et al. | Unique bar-like sulfur-doped C3N4/TiO2 nanocomposite: excellent visible light driven photocatalytic activity and mechanism study | |
| CN106111174A (en) | G C3N4/ kaolinite composite photo-catalyst and preparation method thereof | |
| CN110252326B (en) | Copper tungstate @ zinc oxide composite photocatalyst and preparation method and application thereof | |
| CN109847786A (en) | A kind of preparation method and application of Z-type photochemical catalyst MgAlLDH/CN-H | |
| Xin et al. | Synthesis of ZnS@ CdS–Te composites with p–n heterostructures for enhanced photocatalytic hydrogen production by microwave-assisted hydrothermal method | |
| CN105195197A (en) | TiO2 catalyst with large specific surface area and visible-light response function and method for preparing TiO2 catalyst | |
| CN102895965B (en) | Er<3+>: Y3Al5O12/TiO2 composite membrane and application thereof in catalytic degradation of organic dye | |
| CN107469839A (en) | A kind of preparation method of acid iodide oxygen bismuth photochemical catalyst | |
| CN107570174A (en) | A kind of preparation method and application of efficient stable nickel foam base optic catalytic material | |
| CN102974373A (en) | Visible-light photocatalytic material and preparation method thereof | |
| CN106563477A (en) | Ternary composite visible light photocatalyst, preparation method and application thereof | |
| CN112108150A (en) | Based on magnetic Fe3O4Modified corncob biomass carbon dot composite Bi2WO6Preparation method and application of photocatalyst | |
| CN111437866B (en) | Double-defect heterojunction photocatalyst and preparation method and application thereof | |
| CN109847780A (en) | A kind of AgBr/BiOI/g-C3N4The preparation method and applications of tri compound catalysis material | |
| CN111822027B (en) | Preparation method of titanium dioxide coated carbon nitride composite photocatalytic material | |
| CN110975894A (en) | Visible light response type efficient and stable nano CsPbBr3/TiO2Composite photocatalyst and preparation method thereof | |
| CN105126821B (en) | A kind of flower-shaped Bi2MoO6Preparation and its in photo catalytic reduction CO2In application | |
| CN102794188A (en) | PtC14/Bi2WO6 photocatalyst, and preparation and application thereof | |
| Wu et al. | Fabrication of Bi2MoO6/g-C3N4 visible-light driven photocatalyst for enhanced tetracycline degradation | |
| CN105879855B (en) | A kind of graphene-γ-bismuth molybdate nanocomposite and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20201229 Address after: 443007 No. 66-2 Ting Ting Road, Ting Ting District, Yichang, Hubei Applicant after: HUBEI MOPHOS TECHNOLOGY Co.,Ltd. Address before: 1068 No. 518055 Guangdong city of Shenzhen province Nanshan District Shenzhen University city academy Avenue Applicant before: SHENZHEN INSTITUTES OF ADVANCED TECHNOLOGY CHINESE ACADEMY OF SCIENCES |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |