CN106586987A - Preparation method of black phosphorus nano lamina for photocatalytic degradation of dye wastewater - Google Patents
Preparation method of black phosphorus nano lamina for photocatalytic degradation of dye wastewater Download PDFInfo
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- CN106586987A CN106586987A CN201610962515.9A CN201610962515A CN106586987A CN 106586987 A CN106586987 A CN 106586987A CN 201610962515 A CN201610962515 A CN 201610962515A CN 106586987 A CN106586987 A CN 106586987A
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- black phosphorus
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- nanoscale twins
- multilamellar
- photocatalytic degradation
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 25
- 239000002351 wastewater Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000005119 centrifugation Methods 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract 2
- 239000010919 dye waste Substances 0.000 claims description 18
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 13
- 239000012498 ultrapure water Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 4
- 238000003701 mechanical milling Methods 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 9
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 2
- 239000003086 colorant Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241000446313 Lamella Species 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- -1 black phosphorus alkene Chemical class 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- 244000147568 Laurus nobilis Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
-
- B01J35/39—
-
- B01J35/60—
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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 relates to a preparation method of a black phosphorus nano lamina for photocatalytic degradation of dye wastewater. The method specifically comprises the following steps: (1) preparing multilayer black phosphorus, namely grinding red phosphorus without a surface oxidation layer in a mortar, and then performing mechanical ball milling to obtain the multilayer black phosphorus; and (2) preparing the black phosphorus nano lamina, namely adding the multilayer black phosphorus and a surfactant into water together, performing primary ultrasonic treatment and primary centrifugation, then collecting supernatant, adding the supernatant into water, stirring the materials uniformly, then performing secondary ultrasonic treatment, performing secondary centrifugation to obtain a solid deposit, and drying the solid deposit to obtain the black phosphorus nano lamina. Compared with the prior art, the preparation method provided by the invention is simple in preparation process, high in preparation efficiency, and suitable for large-scale production, and the prepared black phosphorus nano lamina has a higher specific surface area and band gap and photocatalytic activity, and can be used for performing photocatalytic efficient degradation on coloring agents including methylene blue in the dye wastewater.
Description
Technical field
The invention belongs to technical field of nano material, is related to a kind of black phosphorus nanometer sheet for photocatalytic degradation of dye waste water
The preparation method of layer.
Background technology
In recent years, two-dimension nano materials such as Graphene, transient metal sulfide etc., with its excellent physics and architectural characteristic
Outstanding application potential is shown in fields such as electronics, sensing and photoelectric devices.Wherein, Graphene is used as most representative
Two-dimensional material, be widely studied.Graphene has a carrier mobility of superelevation, but while due to a lack of band gap, seriously
Hinder its application in logic semiconductor devices such as field-effect transistor.And as the representative of transient metal sulfide ---
Molybdenum bisuphide (MoS2) with obvious band gap, but there is the reduction that can cause electron mobility again in its fault of construction.
In recent years, the black phosphorus alkene with monolayer or few layer black phosphorus atom Rotating fields, with its higher carrier mobility,
Adjustable direct band gap (determining band gap according to its thickness), larger switch ratio characteristic and anisotropy etc., are increasingly becoming most
Tool potentiality suitable for high-performance electronic and the two-dimension nano materials of opto-electronic device.It is similar with graphite, the atom interlayer of black phosphorus
And be stacked with by faint interlaminar action power, and this active force has Van der Waals force feature, it is therefore provided that machine
Tool is peeled off to be become reliable laboratory technique to prepare minimal amount of high-quality black phosphorus nanoscale twins (as adhesive tape tears point-score).
As black phosphorus nanoscale twins are compared with common multilamellar black phosphorus, with higher specific surface area and band gap, therefore, black phosphorus nanoscale twins
It is more suitably applied to near-infrared and mid-infrared light electric equipment.Additionally, also using the photocatalysis performance of black phosphorus nanoscale twins, preparing
Go out phosphorus thiazolinyl photocatalyst, for efficient degradation waste water from dyestuff, compared with common multilamellar black phosphorus, with more preferable photocatalytic degradation
The performance of the stains such as the methylene blue in waste water from dyestuff.
At present, had scholar to be by mechanically pulling off the technologies such as method, chemical vapour deposition technique, prepare with monolayer or
The black phosphorus alkene of few layer black phosphorus atom Rotating fields.But, it is relatively low that mechanical stripping method prepares yield, is not suitable for for producing business application
Property material, and it is cumbersome, time-consuming；And the preparation amount of chemical vapour deposition technique is considerably less, and it is difficult to repeat.
The content of the invention
The purpose of the present invention is exactly to provide one kind and can effectively improve to overcome the defect of above-mentioned prior art presence
The photocatalytic activity and stability of black phosphorus, and it is adapted to the black phosphorus nanometer sheet for photocatalytic degradation of dye waste water of large-scale production
The preparation method of layer.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, the method specifically includes following
Step：
(1) preparation of multilamellar black phosphorus：The red phosphorus for removing surface oxide layer is placed in mortar and grinds 0.5-1h, obtain multilamellar
Black phosphorus presoma, afterwards by multilamellar black phosphorus presoma rotating speed be 400-600r/min under mechanical ball milling 24-48h, that is, obtain many
Layer black phosphorus；
(2) preparation of black phosphorus nanoscale twins：Multilamellar black phosphorus is added into water together with surfactant, is once surpassed
After sound, mixed solution is obtained, after mixed solution is once centrifuged, collects the supernatant, obtain black phosphorus nanoscale twins forerunner
Body, black phosphorus nanoscale twins presoma is added into water, and twice ultrasonic is carried out after stirring, and is carried out secondary centrifuging afterwards, is obtained
To solid precipitation, after the solid precipitation is dried, that is, obtain described black phosphorus nanoscale twins.
Used as preferred technical scheme, described mortar is agate mortar.
The preparation method of red phosphorus of the removing surface oxide layer described in step (1) is：Red phosphorus is added to water together with water
In hot kettle, 10-15h is reacted at 190-210 DEG C, after reaction terminates, take out solid, be removed after being dried surface oxide layer
Red phosphorus.Steamed by carrying out high warm in water heating kettle to red phosphorus, to remove the oxide layer on red phosphorus surface.
During the red phosphorus for removing surface oxide layer is prepared, in every 1mL water, 0.1-0.2g red phosphorus is added.
In Mechanical Milling Process described in step (1), while be filled with argon being protected, multilamellar black phosphorus presoma quilt is prevented
Oxidation.
In step (2), the quality of described surfactant is the 2.5-5% of multilamellar black phosphorus quality.
In step (2), in a described ultrasonic procedure, the frequency of ultrasound wave is 35-45KHz, and ultrasonic time is 1.5-
2.5h；During described twice ultrasonic, the frequency of ultrasound wave is 35-45KHz, and ultrasonic time is 0.5-1.5h.
In step (2), in step (2), in a described centrifugal process, centrifuge speed is 8000-12000r/min,
Centrifugation time is 8-12min；During described secondary centrifuging, centrifuge speed is 4000-6000r/min, and centrifugation time is
3-8min。
In whipping process described in step (2), blender rotating speed is 400-600r/min, and mixing time is preferably 3-
25min, makes black phosphorus nanoscale twins presoma be dispersed in water.
In step (2), described surfactant include CTAB, SDS, PVP, P123, SDBS, Brij30,
One or more in TritonX100 or Tween80.Wherein, CTAB is cetyl trimethylammonium bromide, and SDS is dodecane
Base sodium sulfate, PVP are polyvinylpyrrolidone, and P123 is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer
Thing, SDBS are dodecylbenzene sodium sulfonate, and Brij30 is polyoxyethylene laurel ether, and TritonX100 is Polyethylene Glycol octyl phenyl
Ether, Tween80 are sorbitan monooleate polyoxyethylene ether.
Used as preferred technical scheme, described surfactant is SDS.
Described water is ultra-pure water.
The present invention is mainly peeled off to multilamellar black phosphorus by surfactant, prepares black phosphorus nanoscale twins.
Compared with prior art, the invention has the characteristics that：
1) with red phosphorus as raw material, multilamellar black phosphorus is first prepared, afterwards surfactant is inserted in multilamellar black phosphorus, made many
Layer black phosphorus layering, and be black phosphorus nanoscale twins by the stripping of multilamellar black phosphorus, preparation process is simple, preparation efficiency height are adapted to scale
Production, using value are high；
2) the black phosphorus nanoscale twins prepared have higher specific surface area and band gap, effectively increase the photocatalysis of black phosphorus
Activity and stability, compared with multilamellar black phosphorus, the black phosphorus nanoscale twins that the present invention is prepared are more suitably applied to near-infrared with
Infrared electro equipment；
3) black phosphorus nanoscale twins can be prepared into phosphorus thiazolinyl photocatalyst, it is for efficient degradation waste water from dyestuff, useless to dyestuff
The stains such as the methylene blue in water carry out photocatalytic degradation.
Description of the drawings
The XRD spectrum of multilamellar black phosphorus of the Fig. 1 to prepare in embodiment 1；
Fig. 2 is the Raman spectrogram of the multilamellar black phosphorus for preparing and black phosphorus nanoscale twins in embodiment 1；
Fig. 3 is the EDS-mapping figures in the TEM collection of illustrative plates of black phosphorus nanoscale twins and TEM prepared in embodiment 1
Spectrum；
The AFM collection of illustrative plates of black phosphorus nanoscale twins of the Fig. 4 to prepare in embodiment 1；
Fig. 5 be in embodiment 1 the multilamellar black phosphorus for preparing and black phosphorus nanoscale twins under xenon lamp irradiation, to methylene blue
The photocatalytic degradation effect figure of solution.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, give detailed embodiment and specific operating process, but protection scope of the present invention be not limited to
Following embodiments.
Embodiment 1：
A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, specifically includes following steps：
(1) preparation of multilamellar black phosphorus：
Using red phosphorus as template, take 2g red phosphorus and 15mL ultra-pure waters are added in the water heating kettle of 25mL together, the heat at 200 DEG C
12h is steamed, for removing the oxide layer on red phosphorus surface.After then taking out and being dried, 0.8h is ground with agate mortar, obtain multilamellar black
Phosphorus presoma, by multilamellar black phosphorus presoma, argon filling gas shielded carries out mechanical ball milling, ball milling 30h, rotating speed at normal temperatures and pressures afterwards
It is maintained at 500r/min.Multilamellar black phosphorus is obtained after the completion of mechanical ball milling.
(2) preparation of black phosphorus nanoscale twins：
Multilamellar black phosphorus and surfactant are pressed into 20:1 mass ratio is mixed in together adding ultra-pure water, by once
Supersound process, obtains the mixed solution of multilamellar black phosphorus and surfactant；Again the mixed solution is once centrifuged, in collection
Layer clear liquid, that is, obtain black phosphorus nanoscale twins presoma, the black phosphorus nanoscale twins presoma added after ultra-pure water again, after stirring
Twice ultrasonic is carried out, then carries out secondary centrifuging, collected solid centrifugation product, after vacuum drying, obtain black phosphorus nanoscale twins.
Fig. 1 is the XRD spectrum of the multilamellar black phosphorus for preparing.In XRD spectrum, 15 °, 34 ° and 55 ° three characteristic peaks difference
(020), (040), (060) crystal face corresponding to multilamellar black phosphorus, it was confirmed that product obtained in red phosphorus is multilamellar black phosphorus.
Fig. 2 is the Raman spectrogram of the multilamellar black phosphorus and black phosphorus nanoscale twins for preparing.In figure, 356cm-1、437cm-1
And 467cm-1Three peaks correspond respectively to black phosphorus, B2g and, and the peak of the black phosphorus nanoscale twins after peeling off is slightly
To high wavelength shift, respectively 360cm-1、440cm-1And 470cm-1.Go out peak position to be sufficiently close to, show obtained black phosphorus nanometer
Compared with multilamellar black phosphorus, material construction itself does not change lamella.
Fig. 3 is the EDS-mapping collection of illustrative plates in the TEM collection of illustrative plates and TEM of the black phosphorus nanoscale twins for preparing.Can from figure
To find out, multilamellar black phosphorus is stripped into as nano-lamellar structure, and lamella contour edge is fairly obvious, and only exists single phosphorus
Element.
Fig. 4 is the AFM collection of illustrative plates of the black phosphorus nanoscale twins for preparing.As can be seen from Figure, peeled off by multilamellar black phosphorus
The black phosphorus nano-lamellar structure that arrives is clear, and its thickness is 3.65nm, and the thickness shows that multilamellar black phosphorus has been stripped and receives for black phosphorus
Rice lamella.
Fig. 5 is the photocatalytic degradation effect of multilamellar black phosphorus and black phosphorus nanoscale twins under xenon lamp irradiation, to methylene blue solution
Fruit is schemed.As can be seen from Figure, the photocatalytic degradation effect of black phosphorus nanoscale twins is more preferable.After 65min, black phosphorus nanoscale twins
It is 65% to the methylene blue degradation rate in methylene blue solution, multilamellar black phosphorus is degraded to the methylene blue in methylene blue solution
Rate is 42%, and both have differed 23%, show that black phosphorus nanoscale twins have more preferable photocatalysis performance.
Embodiment 2：
A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, the method specifically includes following
Step：
(1) preparation of multilamellar black phosphorus：Red phosphorus is added into water heating kettle together with ultra-pure water, wherein, add in every 1mL water
0.1g red phosphorus, reacts 15h afterwards at 190 DEG C, after reaction terminates, takes out solid, and be removed after being dried surface oxide layer
Red phosphorus；The red phosphorus for removing surface oxide layer is placed in mortar and grinds 0.5h, obtain multilamellar black phosphorus presoma, it is afterwards that multilamellar is black
Phosphorus presoma is mechanical ball milling under 400r/min in rotating speed, while be filled with argon being protected, prevents multilamellar black phosphorus presoma quilt
Oxidation, after 48h, that is, obtains multilamellar black phosphorus；
(2) preparation of black phosphorus nanoscale twins：From SDS as surfactant, by multilamellar black phosphorus and surfactant one
Rise and add into ultra-pure water, wherein, the quality of surfactant is the 2.5% of multilamellar black phosphorus quality.(surpass after carrying out once ultrasound
The frequency of sound wave is 35KHz, and ultrasonic time is 2.5h), mixed solution is obtained, (centrifugation after mixed solution is once centrifuged
Machine rotating speed is 8000r/min, and centrifugation time is 12min), the supernatant is collected, black phosphorus nanoscale twins presoma is obtained, by black phosphorus
Nanoscale twins presoma is added into ultra-pure water, after being to stir under 400r/min in blender rotating speed, carries out twice ultrasonic
(frequency of ultrasound wave be 35KHz, ultrasonic time is 1.5h), carry out afterwards secondary centrifuging (centrifuge speed is 4000r/min,
Centrifugation time is 8min), solid precipitation is obtained, after the solid precipitation is dried, that is, black phosphorus nanoscale twins is obtained.
Embodiment 3：
A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, the method specifically includes following
Step：
(1) preparation of multilamellar black phosphorus：Red phosphorus is added into water heating kettle together with ultra-pure water, wherein, add in every 1mL water
0.2g red phosphorus, reacts 10h afterwards at 210 DEG C, after reaction terminates, takes out solid, and be removed after being dried surface oxide layer
Red phosphorus；The red phosphorus for removing surface oxide layer is placed in mortar and grinds 1h, obtain multilamellar black phosphorus presoma, afterwards by multilamellar black phosphorus
Presoma is mechanical ball milling under 600r/min in rotating speed, while be filled with argon being protected, prevents multilamellar black phosphorus presoma by oxygen
Change, after 24h, that is, obtain multilamellar black phosphorus；
(2) preparation of black phosphorus nanoscale twins：From CTAB as surfactant, by multilamellar black phosphorus and surfactant one
Rise and add into ultra-pure water, wherein, the quality of surfactant is the 5% of multilamellar black phosphorus quality.Carry out (ultrasound after once ultrasound
The frequency of ripple is 45KHz, and ultrasonic time is 1.5h), mixed solution is obtained, (centrifuge after mixed solution is once centrifuged
Rotating speed is 12000r/min, and centrifugation time is 8min), the supernatant is collected, black phosphorus nanoscale twins presoma is obtained, black phosphorus is received
Rice lamella presoma is added into ultra-pure water, after being to stir under 600r/min in blender rotating speed, carries out twice ultrasonic (super
The frequency of sound wave is 45KHz, and ultrasonic time is 0.5h), (centrifuge speed is 6000r/min, centrifugation to carry out secondary centrifuging afterwards
Time is 3min), solid precipitation is obtained, after the solid precipitation is dried, that is, black phosphorus nanoscale twins is obtained.
Embodiment 4：
A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, the method specifically includes following
Step：
(1) preparation of multilamellar black phosphorus：Red phosphorus is added into water heating kettle together with ultra-pure water, wherein, add in every 1mL water
0.13g red phosphorus, reacts 12h afterwards at 200 DEG C, after reaction terminates, takes out solid, and be removed after being dried surface oxide layer
Red phosphorus；The red phosphorus for removing surface oxide layer is placed in mortar and grinds 0.7h, obtain multilamellar black phosphorus presoma, it is afterwards that multilamellar is black
Phosphorus presoma is mechanical ball milling under 500r/min in rotating speed, while be filled with argon being protected, prevents multilamellar black phosphorus presoma quilt
Oxidation, after 35h, that is, obtains multilamellar black phosphorus；
(2) preparation of black phosphorus nanoscale twins：From PVP as surfactant, by multilamellar black phosphorus and surfactant one
Rise and add into ultra-pure water, wherein, the quality of surfactant is the 3.5% of multilamellar black phosphorus quality.(surpass after carrying out once ultrasound
The frequency of sound wave is 40KHz, and ultrasonic time is 2h), mixed solution is obtained, (centrifuge after mixed solution is once centrifuged
Rotating speed is 10000r/min, and centrifugation time is 10min), the supernatant is collected, black phosphorus nanoscale twins presoma is obtained, by black phosphorus
Nanoscale twins presoma is added into ultra-pure water, after being to stir under 500r/min in blender rotating speed, carries out twice ultrasonic
(frequency of ultrasound wave be 40KHz, ultrasonic time is 1h), carry out afterwards secondary centrifuging (centrifuge speed is 5000r/min, from
The heart time is 5min), solid precipitation is obtained, after the solid precipitation is dried, that is, black phosphorus nanoscale twins is obtained.
Embodiment 5：
In the present embodiment, surfactant selects P123, and remaining is with embodiment 2.
Embodiment 6：
In the present embodiment, surfactant selects SDBS, and remaining is with embodiment 2.
Embodiment 7：
In the present embodiment, surfactant selects Brij30, and remaining is with embodiment 2.
Embodiment 8：
In the present embodiment, surfactant selects TritonX100, and remaining is with embodiment 2.
Embodiment 9：
In the present embodiment, surfactant selects Tween80, and remaining is with embodiment 2.
Embodiment 10：
In the present embodiment, surfactant includes CTAB and SDS, and remaining is with embodiment 2.
Embodiment 11：
In the present embodiment, surfactant includes PVP, P123 and Brij30, and remaining is with embodiment 2.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and use invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel announcement of the invention, the improvement made without departing from scope and modification all should be the present invention's
Within protection domain.
Claims (10)
1. a kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, it is characterised in that the method has
Body is comprised the following steps：
(1) preparation of multilamellar black phosphorus：The red phosphorus for removing surface oxide layer is placed in mortar and grinds 0.5-1h, obtain multilamellar black phosphorus
Presoma, afterwards by multilamellar black phosphorus presoma rotating speed be 400-600r/min under mechanical ball milling 24-48h, that is, obtain multilamellar black
Phosphorus；
(2) preparation of black phosphorus nanoscale twins：Multilamellar black phosphorus is added into water together with surfactant, once ultrasound is carried out
Afterwards, mixed solution is obtained, after mixed solution is once centrifuged, collects the supernatant, obtain black phosphorus nanoscale twins presoma,
Black phosphorus nanoscale twins presoma is added into water, twice ultrasonic after stirring, is carried out, secondary centrifuging is carried out afterwards, consolidate
Body is precipitated, and after the solid precipitation is dried, that is, obtains described black phosphorus nanoscale twins.
2. the preparation method of a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
Characterized in that, the preparation method of the red phosphorus for removing surface oxide layer described in step (1) is：Red phosphorus is added together with water to
In water heating kettle, 10-15h is reacted at 190-210 DEG C, after reaction terminates, take out solid, be removed after being dried surface oxidation
The red phosphorus of layer.
3. the preparation method of a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 2,
Characterized in that, during the red phosphorus for removing surface oxide layer is prepared, adding 0.1-0.2g red phosphorus in every 1mL water.
4. the preparation method of a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
Characterized in that, in Mechanical Milling Process described in step (1), while be filled with argon being protected, preventing multilamellar black phosphorus forerunner
Body is oxidized.
5. the preparation method of a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
Characterized in that, in step (2), the quality of described surfactant is the 2.5-5% of multilamellar black phosphorus quality.
6. the preparation method of a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
Characterized in that, in step (2), in a described ultrasonic procedure, the frequency of ultrasound wave is 35-45KHz, and ultrasonic time is
1.5-2.5h；During described twice ultrasonic, the frequency of ultrasound wave is 35-45KHz, and ultrasonic time is 0.5-1.5h.
7. the preparation method of a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
Characterized in that, in step (2), in a described centrifugal process, centrifuge speed is 8000-12000r/min, during centrifugation
Between be 8-12min；During described secondary centrifuging, centrifuge speed is 4000-6000r/min, and centrifugation time is 3-8min.
8. the preparation method of a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
Characterized in that, in whipping process described in step (2), blender rotating speed is 400-600r/min.
9. a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to any one of claim 1 to 8
Preparation method, it is characterised in that in step (2), described surfactant include CTAB, SDS, PVP, P123, SDBS,
One or more in Brij30, TritonX100 or Tween80.
10. a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to any one of claim 1 to 8
Preparation method, it is characterised in that described water is ultra-pure water.
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