CN106586987B - A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water - Google Patents
A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 23
- 239000010919 dye waste Substances 0.000 title claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000005119 centrifugation Methods 0.000 claims abstract description 11
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 238000002604 ultrasonography Methods 0.000 claims abstract description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 14
- 239000012498 ultrapure water Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 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
- 239000007789 gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 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
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 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
- 238000001035 drying Methods 0.000 claims description 2
- 238000003701 mechanical milling Methods 0.000 claims description 2
- 238000010301 surface-oxidation reaction Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000000975 dye Substances 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 21
- 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 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 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
- -1 black phosphorus alkene Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 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
- 229920003171 Poly (ethylene oxide) Polymers 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000463 material Substances 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
- 229910052982 molybdenum disulfide Inorganic materials 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005669 field effect Effects 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
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 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
- 229920001155 polypropylene 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
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 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 present invention relates to a kind of preparation methods of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, this method specifically includes the following steps: (1) multilayer black phosphorus preparation: the red phosphorus for removing surface oxide layer is placed in mortar and is ground, mechanical ball mill is carried out later, obtains multilayer black phosphorus；(2) preparation of black phosphorus nanoscale twins: multilayer black phosphorus is added together with surfactant into water, after carrying out primary ultrasound and primary centrifugation, it collects supernatant liquor and is added into water, twice ultrasonic is carried out after mixing evenly, again after secondary centrifuging, solid precipitating is obtained, arrives black phosphorus nanoscale twins after solid precipitating is dried.Compared with prior art; preparation process of the present invention is simple, and preparation efficiency is high, is suitble to large-scale production; and the black phosphorus nanoscale twins prepared have higher specific surface area and band gap and photocatalytic activity, carry out photocatalysis efficient degradation to coloring agents such as methylene blues in waste water from dyestuff.
Description
Technical field
The invention belongs to technical field of nano material, are related to a kind of black phosphorus nanometer sheet for photocatalytic degradation of dye waste water
The preparation method of layer.
Background technique
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 conduct is most representative
Two-dimensional material, be widely studied.Graphene has the carrier mobility of superelevation, but simultaneously due to a lack of band gap, seriously
Hinder its application in logic semiconductor devices such as field effect transistor.And the representative as transient metal sulfide ---
Molybdenum disulfide (MoS2) there is apparent band gap, but there is the reduction that will lead to electron mobility again in its fault of construction.
In recent years, the black phosphorus alkene with single layer or few layer black phosphorus atomic layer structure, with its higher carrier mobility,
Adjustable direct band gap (determining band gap according to its thickness), biggish switch ratio characteristic and anisotropy etc., are increasingly becoming most
Have the two-dimension nano materials suitable for high-performance electronic and opto-electronic device of potentiality.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 removing (such as adhesive tape tears point-score) becomes reliable laboratory technique to prepare minimal amount of high quality black phosphorus nanoscale twins.
Since black phosphorus nanoscale twins are compared with common multilayer black phosphorus, there is 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.In addition, also using the photocatalysis performance of black phosphorus nanoscale twins, preparation
Phosphorus alkenyl photochemical catalyst out is used for efficient degradation waste water from dyestuff, compared with common multilayer black phosphorus, has better photocatalytic degradation
The performance of the coloring agents such as the methylene blue in waste water from dyestuff.
Currently, there is scholar to be by mechanically pulling off the technologies such as method, chemical vapour deposition technique, prepare with single layer or
The black phosphorus alkene of few layer black phosphorus atomic layer structure.But to prepare yield lower for mechanical stripping method, is not suitable for being used to produce business application
Property material, and it is cumbersome, time-consuming；And the preparation amount of chemical vapour deposition technique is considerably less, and is not easy to repeat.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind to effectively improve
The photocatalytic activity and stability of black phosphorus, and it is suitble 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, this method specifically includes following
Step:
(1) preparation of multilayer black phosphorus: the red phosphorus for removing surface oxide layer is placed in mortar and grinds 0.5-1h, obtains multilayer
Black phosphorus presoma, by multilayer black phosphorus presoma, in the case where revolving speed is 400-600r/min, mechanical ball mill 24-48h is more to get arriving later
Layer black phosphorus；
(2) preparation of black phosphorus nanoscale twins: multilayer black phosphorus is added together with surfactant into water, is once surpassed
After sound, mixed solution is obtained, mixed solution is carried out after being once centrifuged, supernatant liquor is collected, obtains black phosphorus nanoscale twins forerunner
Black phosphorus nanoscale twins presoma is added into water, carries out twice ultrasonic after mixing evenly, carries out secondary centrifuging later, obtain by body
It is precipitated to solid, arrives the black phosphorus nanoscale twins after solid precipitating is dried.
The mortar is agate mortar as a preferred technical solution,.
Described in step (1) remove surface oxide layer red phosphorus the preparation method comprises the following steps: being added red phosphorus together with water to water
In hot kettle, 10-15h is reacted at 190-210 DEG C, after reaction, takes out solid, be removed surface oxide layer after dry
Red phosphorus.It is steamed by carrying out high warm to red phosphorus in water heating kettle, to remove the oxide layer on red phosphorus surface.
During preparation removes the red phosphorus of surface oxide layer, 0.1-0.2g red phosphorus is added in every 1mL water.
It in Mechanical Milling Process described in step (1), while being filled with argon gas and being protected, prevent multilayer black phosphorus presoma quilt
Oxidation.
In step (2), the quality of the surfactant is the 2.5-5% of multilayer black phosphorus quality.
In step (2), in a ultrasonic procedure, the frequency of ultrasonic wave is 35-45KHz, ultrasonic time 1.5-
2.5h；During the twice ultrasonic, the frequency of ultrasonic wave is 35-45KHz, ultrasonic time 0.5-1.5h.
In step (2), in step (2), in a centrifugal process, centrifuge speed 8000-12000r/min,
Centrifugation time is 8-12min；During the secondary centrifuging, centrifuge speed 4000-6000r/min, centrifugation time is
3-8min。
In whipping process described in step (2), blender revolving speed is 400-600r/min, and mixing time is preferably 3-
25min is dispersed in black phosphorus nanoscale twins presoma in water.
In step (2), the surfactant include CTAB, SDS, PVP, P123, SDBS, Brij30,
One of TritonX100 or Tween80 or a variety of.Wherein, CTAB is cetyl trimethylammonium bromide, and SDS is dodecane
Base sodium sulphate, PVP are polyvinylpyrrolidone, and P123 is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer
Object, SDBS are neopelex, and Brij30 is polyoxyethylene laurel ether, and TritonX100 is polyethylene glycol octyl phenyl
Ether, Tween80 are sorbitan monooleate polyoxyethylene ether.
The surfactant is SDS as a preferred technical solution,.
The water is ultrapure water.
The present invention mainly passes through surfactant and removes to multilayer black phosphorus, prepares black phosphorus nanoscale twins.
Compared with prior art, the invention has the characteristics that:
1) using red phosphorus as raw material, multilayer black phosphorus is first prepared, surfactant is inserted into multilayer black phosphorus later, is made more
Layer black phosphorus layering, and multilayer black phosphorus remove as black phosphorus nanoscale twins, preparation process is simple, preparation efficiency height, suitable scale
Production, application 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 multilayer black phosphorus, the black phosphorus nanoscale twins that the present invention prepares are more suitably applied to near-infrared in
Infrared electro equipment；
3) black phosphorus nanoscale twins can be prepared into phosphorus alkenyl photochemical catalyst, be used for efficient degradation waste water from dyestuff, it is useless to dyestuff
The coloring agents such as the methylene blue in water carry out photocatalytic degradation.
Detailed description of the invention
Fig. 1 is the XRD spectrum for the multilayer black phosphorus being prepared in embodiment 1；
Fig. 2 is the Raman spectrogram of the multilayer black phosphorus and black phosphorus nanoscale twins that are prepared in embodiment 1；
Fig. 3 is the TEM map for the black phosphorus nanoscale twins being prepared in embodiment 1 and the EDS-mapping figure in TEM
Spectrum；
Fig. 4 is the AFM map for the black phosphorus nanoscale twins being prepared in embodiment 1；
Fig. 5 is the multilayer black phosphorus being prepared in embodiment 1 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, the detailed implementation method and specific operation process are given, but protection scope of the present invention is 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 the following steps:
(1) preparation of multilayer black phosphorus:
Using red phosphorus as template, 2g red phosphorus and 15mL ultrapure water is taken to be added in the water heating kettle of 25mL together, it is hot at 200 DEG C
12h is steamed, for removing the oxide layer on red phosphorus surface.After then taking out and drying, 0.8h is ground with agate mortar, it is black to obtain multilayer
Phosphorus presoma, by multilayer black phosphorus presoma, argon filling gas shielded carries out mechanical ball mill, ball milling 30h, revolving speed at normal temperatures and pressures later
It is maintained at 500r/min.Multilayer black phosphorus is obtained after the completion of mechanical ball mill.
(2) preparation of black phosphorus nanoscale twins:
Multilayer black phosphorus and surfactant are added in ultrapure water together by the mass ratio of 20:1 and mixed, by primary
Ultrasonic treatment, obtains the mixed solution of multilayer black phosphorus and surfactant；The mixed solution is once centrifuged again, in collection
Layer clear liquid is to get black phosphorus nanoscale twins presoma is arrived, after which is added ultrapure water again, after mixing evenly
Twice ultrasonic is carried out, then carries out secondary centrifuging, solid is collected and is centrifuged product, black phosphorus nanoscale twins are obtained after vacuum drying.
Fig. 1 is the XRD spectrum for the multilayer black phosphorus being prepared.In XRD spectrum, 15 °, 34 ° and 55 ° three characteristic peaks difference
Corresponding to (020) of multilayer black phosphorus, (040), (060) crystal face, it was confirmed that product made from red phosphorus is multilayer black phosphorus.
Fig. 2 is the multilayer black phosphorus being prepared and the Raman spectrogram of black phosphorus nanoscale twins.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 removing is slightly
To high wavelength shift, respectively 360cm-1、440cm-1And 470cm-1.Peak position is very close out, shows black phosphorus nanometer obtained
Compared with multilayer black phosphorus, substance itself constructs not to change lamella.
The TEM map and the EDS-mapping map in TEM that Fig. 3 is the black phosphorus nanoscale twins being prepared.It can from figure
To find out, multilayer 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 map for the black phosphorus nanoscale twins being prepared.As can be seen from Figure, it is removed by multilayer black phosphorus
The black phosphorus nano-lamellar structure arrived is clear, and with a thickness of 3.65nm, which shows that multilayer black phosphorus has been stripped and receive for black phosphorus
Rice lamella.
Fig. 5 is multilayer black phosphorus and black phosphorus nanoscale twins under xenon lamp irradiation, is imitated to the photocatalytic degradation of methylene blue solution
Fruit figure.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, multilayer black phosphorus degrades to the methylene blue in methylene blue solution
Rate is 42%, and the two has differed 23%, shows that black phosphorus nanoscale twins have better photocatalysis performance.
Embodiment 2:
A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, this method specifically includes following
Step:
(1) preparation of multilayer black phosphorus: red phosphorus is added together with ultrapure water into water heating kettle, wherein be added in every 1mL water
0.1g red phosphorus reacts 15h at 190 DEG C later, after reaction, takes out solid, be removed surface oxide layer after dry
Red phosphorus；The red phosphorus for removing surface oxide layer is placed in mortar and grinds 0.5h, obtains multilayer black phosphorus presoma, it is later that multilayer is black
Phosphorus presoma mechanical ball mill in the case where revolving speed is 400r/min, while being filled with argon gas and being protected, prevent multilayer black phosphorus presoma quilt
It aoxidizes, arrives multilayer black phosphorus after 48h；
(2) preparation of black phosphorus nanoscale twins: select SDS as surfactant, by multilayer black phosphorus and surfactant one
It rises and is added into ultrapure water, wherein the quality of surfactant is the 2.5% of multilayer black phosphorus quality.(surpass after carrying out primary ultrasound
The frequency of sound wave is 35KHz, ultrasonic time 2.5h), mixed solution is obtained, mixed solution is subjected to (centrifugation after being once centrifuged
Machine revolving speed is 8000r/min, centrifugation time 12min), supernatant liquor is collected, black phosphorus nanoscale twins presoma is obtained, by black phosphorus
Nanoscale twins presoma is added into ultrapure water, after mixing evenly in the case where blender revolving speed is 400r/min, carries out twice ultrasonic
(frequency of ultrasonic wave be 35KHz, ultrasonic time 1.5h), carry out later secondary centrifuging (centrifuge speed 4000r/min,
Centrifugation time is 8min), solid precipitating is obtained, arrives black phosphorus nanoscale twins after solid precipitating is dried.
Embodiment 3:
A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, this method specifically includes following
Step:
(1) preparation of multilayer black phosphorus: red phosphorus is added together with ultrapure water into water heating kettle, wherein be added in every 1mL water
0.2g red phosphorus reacts 10h at 210 DEG C later, after reaction, takes out solid, be removed surface oxide layer after dry
Red phosphorus；The red phosphorus for removing surface oxide layer is placed in mortar and grinds 1h, obtains multilayer black phosphorus presoma, later by multilayer black phosphorus
Presoma mechanical ball mill in the case where revolving speed is 600r/min, while being filled with argon gas and being protected, prevent multilayer black phosphorus presoma by oxygen
Change, for 24 hours after to get arrive multilayer black phosphorus；
(2) preparation of black phosphorus nanoscale twins: select CTAB as surfactant, by multilayer black phosphorus and surfactant one
It rises and is added into ultrapure water, wherein the quality of surfactant is the 5% of multilayer black phosphorus quality.(ultrasound after the primary ultrasound of progress
The frequency of wave is 45KHz, ultrasonic time 1.5h), mixed solution is obtained, mixed solution is subjected to (centrifuge after being once centrifuged
Revolving speed is 12000r/min, centrifugation time 8min), supernatant liquor is collected, black phosphorus nanoscale twins presoma is obtained, black phosphorus is received
Rice lamella presoma is added into ultrapure water, after mixing evenly in the case where blender revolving speed is 600r/min, it is (super to carry out twice ultrasonic
The frequency of sound wave is 45KHz, ultrasonic time 0.5h), secondary centrifuging (centrifuge speed 6000r/min, centrifugation are carried out later
Time is 3min), solid precipitating is obtained, arrives black phosphorus nanoscale twins after solid precipitating is dried.
Embodiment 4:
A kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, this method specifically includes following
Step:
(1) preparation of multilayer black phosphorus: red phosphorus is added together with ultrapure water into water heating kettle, wherein be added in every 1mL water
0.13g red phosphorus reacts 12h at 200 DEG C later, after reaction, takes out solid, be removed surface oxide layer after dry
Red phosphorus；The red phosphorus for removing surface oxide layer is placed in mortar and grinds 0.7h, obtains multilayer black phosphorus presoma, it is later that multilayer is black
Phosphorus presoma mechanical ball mill in the case where revolving speed is 500r/min, while being filled with argon gas and being protected, prevent multilayer black phosphorus presoma quilt
It aoxidizes, arrives multilayer black phosphorus after 35h；
(2) preparation of black phosphorus nanoscale twins: select PVP as surfactant, by multilayer black phosphorus and surfactant one
It rises and is added into ultrapure water, wherein the quality of surfactant is the 3.5% of multilayer black phosphorus quality.(surpass after carrying out primary ultrasound
The frequency of sound wave is 40KHz, ultrasonic time 2h), mixed solution is obtained, mixed solution is subjected to (centrifuge after being once centrifuged
Revolving speed is 10000r/min, centrifugation time 10min), supernatant liquor is collected, black phosphorus nanoscale twins presoma is obtained, by black phosphorus
Nanoscale twins presoma is added into ultrapure water, after mixing evenly in the case where blender revolving speed is 500r/min, carries out twice ultrasonic
(frequency of ultrasonic wave be 40KHz, ultrasonic time 1h), carry out later secondary centrifuging (centrifuge speed 5000r/min, from
The heart time is 5min), obtain solid precipitating, by solid precipitating it is dry after to get arriving black phosphorus nanoscale twins.
Embodiment 5:
In the present embodiment, surfactant selects P123, remaining is the same as embodiment 2.
Embodiment 6:
In the present embodiment, surfactant selects SDBS, remaining is the same as embodiment 2.
Embodiment 7:
In the present embodiment, surfactant selects Brij30, remaining is the same as embodiment 2.
Embodiment 8:
In the present embodiment, surfactant selects TritonX100, remaining is the same as embodiment 2.
Embodiment 9:
In the present embodiment, surfactant selects Tween80, remaining is the same as embodiment 2.
Embodiment 10:
In the present embodiment, surfactant includes CTAB and SDS, remaining is the same as embodiment 2.
Embodiment 11:
In the present embodiment, surfactant includes PVP, P123 and Brij30, remaining is the same as embodiment 2.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (8)
1. a kind of preparation method of the black phosphorus nanoscale twins for photocatalytic degradation of dye waste water, which is characterized in that this method tool
Body the following steps are included:
(1) preparation of multilayer black phosphorus: the red phosphorus for removing surface oxide layer being placed in mortar and grinds 0.5-1h, obtains multilayer black phosphorus
Presoma, by multilayer black phosphorus presoma, in the case where revolving speed is 400-600r/min, mechanical ball mill 24-48h is black to get multilayer is arrived later
Phosphorus；
(2) preparation of black phosphorus nanoscale twins: multilayer black phosphorus is added together with surfactant into water, carries out primary ultrasound
Afterwards, mixed solution is obtained, mixed solution is carried out after being once centrifuged, supernatant liquor is collected, obtains black phosphorus nanoscale twins presoma,
Black phosphorus nanoscale twins presoma is added into water, carries out twice ultrasonic after mixing evenly, carries out secondary centrifuging later, consolidate
Body precipitating arrives the black phosphorus nanoscale twins after drying solid precipitating；
In step (2), the quality of the surfactant is the 2.5-5% of multilayer black phosphorus quality；
In step (2), the surfactant be CTAB, SDS, PVP, P123, SDBS, Brij30, TritonX100 and
One of Tween80 or a variety of.
2. a kind of preparation method of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
It is characterized in that, described in step (1) remove surface oxide layer red phosphorus the preparation method comprises the following steps: red phosphorus is added together with water to
In water heating kettle, 10-15h is reacted at 190-210 DEG C, after reaction, takes out solid, be removed surface oxidation after dry
The red phosphorus of layer.
3. a kind of preparation method of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 2,
It is characterized in that, 0.1-0.2g red phosphorus is added in every 1mL water during preparation removes the red phosphorus of surface oxide layer.
4. a kind of preparation method of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
It is characterized in that, in Mechanical Milling Process described in step (1), while being filled with argon gas and being protected, prevent multilayer black phosphorus forerunner
Body is oxidized.
5. a kind of preparation method of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
It is characterized in that, in a ultrasonic procedure, the frequency of ultrasonic wave is 35-45KHz, and ultrasonic time is in step (2)
1.5-2.5h；During the twice ultrasonic, the frequency of ultrasonic wave is 35-45KHz, ultrasonic time 0.5-1.5h.
6. a kind of preparation method of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
It is characterized in that, in step (2), in a centrifugal process, centrifuge speed 8000-12000r/min, when centrifugation
Between be 8-12min；During the secondary centrifuging, centrifuge speed 4000-6000r/min, centrifugation time 3-8min.
7. a kind of preparation method of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to claim 1,
It is characterized in that, blender revolving speed is 400-600r/min in whipping process described in step (2).
8. a kind of black phosphorus nanoscale twins for photocatalytic degradation of dye waste water according to any one of claims 1 to 7
Preparation method, which is characterized in that the water is ultrapure water.
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| CN107117590B (en) * | 2017-06-14 | 2019-01-29 | 合肥工业大学 | A kind of method that gradient sphere grinding prepares two-dimentional black phosphorus |
| CN108515186A (en) * | 2018-05-15 | 2018-09-11 | 中国工程物理研究院化工材料研究所 | The bismuth alkene of surfactant auxiliary, the liquid phase ultrasound stripping means of antimony alkene, black phosphorus |
| CN111137867A (en) * | 2018-11-06 | 2020-05-12 | 湖南工业大学 | Preparation method of surfactant-mediated few-layer black phosphorus nanosheet |
| CN109455790A (en) * | 2018-11-27 | 2019-03-12 | 合肥工业大学 | A method of utilizing two-dimentional black phosphorus material efficient degradation organic pollutant |
| CN109647449A (en) * | 2019-01-21 | 2019-04-19 | 合肥工业大学 | The preparation of a kind of nanometer of modified by silver two dimension black phosphorus composite material and its application of high efficiency photocatalysis degradation antibiotic pollutant |
| CN110040813A (en) * | 2019-04-23 | 2019-07-23 | 中国科学院沈阳应用生态研究所 | A method of polluted-water is handled using two-dimensional layer black phosphorus |
| CN110714224B (en) * | 2019-09-17 | 2021-06-22 | 南京理工大学 | Preparation method of large-area high-stability single-layer blue phospholene based on molecular beam epitaxial growth |
| CN111440651B (en) * | 2020-04-30 | 2022-01-28 | 西安建筑科技大学 | Preparation method of black phosphorus alkene/graphene oxide composite water-based lubricant additive |
| CN111807339B (en) * | 2020-07-24 | 2022-04-05 | 大连海事大学 | Water-based preparation method of black phosphorus quantum dots |
| CN113401884B (en) * | 2021-06-29 | 2022-10-14 | 厦门大学 | Preparation method of surface functionalized two-dimensional black phosphorus nanosheet with asymmetric structure |
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