WO2019128247A1 - Bismuthene nanosheets and preparation method therefor - Google Patents

Bismuthene nanosheets and preparation method therefor Download PDF

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WO2019128247A1
WO2019128247A1 PCT/CN2018/099566 CN2018099566W WO2019128247A1 WO 2019128247 A1 WO2019128247 A1 WO 2019128247A1 CN 2018099566 W CN2018099566 W CN 2018099566W WO 2019128247 A1 WO2019128247 A1 WO 2019128247A1
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terpene
nanosheet
ultrasonic
preparation
water bath
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PCT/CN2018/099566
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Chinese (zh)
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张晗
黄浩
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深圳大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0551—Flake form nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/068—Flake-like particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the invention relates to the field of two-dimensional materials, in particular to a terpene nanosheet and a preparation method thereof.
  • Two-dimensional materials refer to materials that can move freely (planar motion) on two non-nanoscales (1-100 nm), such as nanofilms.
  • black phosphorus (phosphene) phosphene
  • silene terpene
  • decene boron nitride
  • molybdenum disulfide molybdenum disulfide
  • Bismuthene is a two-dimensional material that is stripped from a bulk metal tantalum and has a graphene-like structure.
  • the terpene is a direct bandgap semiconductor with a 0.306 eV energy gap (the bottom of the conduction band and the top of the valence band are at the same position), and can be directly coupled with light, and has a wide absorption spectrum.
  • terpene due to its high biocompatibility and low biotoxicity, terpene has broad application potential in optics, electricity, biomedicine and other fields.
  • the two-dimensional terpene sheet structure is a potential biomedical base material in the fields of biopharmaceutical, photothermal, photodynamic therapy and the like.
  • a sheet of terpene material is prepared by a mechanical peeling method (such as a transparent tape tearing method), a chemical vapor deposition method, or the like.
  • the sheet-like terpene material prepared by the mechanical exfoliation method has a low yield, is not suitable for commercial production, and is cumbersome and time consuming to operate; and the amount of terpene prepared by chemical vapor deposition is small and difficult to repeat.
  • the present invention provides a terpene nanosheet and a preparation method thereof, which combines ultrasonication of a probe with ultrasonication of a water bath to achieve separation of tantalum powder by synergistic action, and obtains good monodispersity and size.
  • the method has the advantages of simple and easy operation, good reproducibility, high yield or yield of the terpene nanosheets, and easy realization of low-cost industrial production.
  • the present invention provides a method for preparing a terpene nanosheet, comprising the steps of:
  • the first water bath ultrasonic power is 400-600 W, the time is 1-6 hours; and the probe ultrasonic 10 is performed at a power of 1080-1800 W. - 24 hours, obtaining a first ultrasonic solution;
  • the organic solvent comprises N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, tetrahydrofuran, absolute ethanol, methanol, isopropanol, One or more of chloroform and dichloromethane, but is not limited thereto.
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • DMSO dimethyl sulfoxide
  • acetone tetrahydrofuran
  • absolute ethanol absolute ethanol
  • methanol methanol
  • isopropanol isopropanol
  • chloroform and dichloromethane is not limited thereto.
  • the surface energy of the organic solvent used matches the surface energy of the two-dimensional layered terpene material, and there is a certain interaction between the two to balance the energy required to remove the tantalum powder.
  • the tantalum powder has a particle size of no more than 75 ⁇ m.
  • the particle size of the tantalum powder does not exceed 50 ⁇ m.
  • the power of the first water bath ultrasound may be 400W, 450W, 500W, 550W, 580W or 600W.
  • the power of the first water bath ultrasound is 420-600W.
  • the second bath is sonicated for a period of from 1 to 6 hours. Further optional is 1-3 hours.
  • the power of the second water bath ultrasound may be 400W, 450W, 500W, 550W, 580W or 600W.
  • the power of the second water bath ultrasound is 420-600W.
  • the power or time of the second water bath ultrasound may be the same or different than the power or time of the first water bath ultrasound.
  • the power of the probe-type ultrasound may be 1100W, 1200W, 1300W, 1400W, 1500W, 1600W or 1700W.
  • the probe-type ultrasound has a power of 1200-1700W.
  • the time of the probe-type ultrasound may be 10h, 12h, 15h, 20h or 24h.
  • the time of the probe-type ultrasound is 12-24 hours.
  • the probe-type ultrasound is performed in an ice bath condition at a temperature not exceeding 10 °C.
  • the temperature at the time of the probe-type ultrasonic wave is 0 to 10 ° C, and more preferably 4 to 10 ° C.
  • the ice bath condition means that the container containing the solution to be ultrasonicated is placed in another container (such as a beaker, a test tube) containing ice cubes during the probe-type ultrasonic process.
  • the first water bath sonication is performed at a temperature of 5-10 °C.
  • the second water bath sonication is carried out at a temperature of 5-10 °C.
  • the ultra-low speed centrifugation has a centrifugation time of 15-30 min. For example, 12, 15, 20, 25 or 30 min.
  • the ultra low speed centrifugation speed is 2000-3000 rpm.
  • the centrifugation time of the low speed centrifugation is 15-30 min.
  • the centrifugation time of the low speed centrifugation is 15-30 min.
  • the low speed centrifugation speed is 6000-7000 rpm.
  • the precipitate obtained after the low-speed centrifugation (i.e., the terpene nanosheet) can be redispersed into the second solvent to obtain a solution containing the terpene nanosheet.
  • the second solvent comprises N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, tetrahydrofuran, absolute ethanol, methanol and isopropanol. One or more of them.
  • the first water bath ultrasonic wave of the bismuth powder dispersion liquid is initially broken by the ultrasonic vacuolar effect, and partially dissolved into the organic solvent, thereby avoiding direct use of the probe type ultrasonic on the probe type ultrasonic system. Loss, prolong the ultrasonic time; the next probe-type ultrasound is to break up the initially broken strontium powder and peel it into a layer structure of decene, so that it is dissolved in organic solvent; the last second water bath Ultrasound can further break up the exfoliated terpene layered material into smaller particles to obtain a terpene nanosheet, and further ensure that it does not agglomerate for subsequent centrifugal purification treatment.
  • the method for preparing a terpene nanosheet provided by the first aspect of the invention, the liquid phase stripping method combining probe ultrasonic and water bath ultrasonic, synergistically to achieve stripping of tantalum powder, the method is simple and easy to operate, and the yield is Higher, compared with the current mechanical stripping method and chemical vapor deposition method, it has obvious advantages, and can obtain a monodisperse terpene nanosheet with controllable size and easy to realize low-cost industrial production. This lays the foundation for the application of terpene nanosheets in the biomedical field.
  • the present invention also provides a terpene nanosheet prepared by the above preparation method.
  • the terpene nanosheet has a thickness of 20 nm or less, and the terpene nanosheet has a lateral dimension of 100 nm to 10 ⁇ m.
  • the lateral dimension refers to the length or width of the terpene nanosheet.
  • the terpene nanosheet has a lateral dimension of 200 nm to 10 ⁇ m.
  • it is 300 nm, 500 nm, 800 nm, 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 8 ⁇ m or 10 ⁇ m.
  • the terpene nanosheet has a lateral dimension of 500 nm to 10 ⁇ m.
  • the terpene nanosheets have a lateral dimension of from 1 ⁇ m to 10 ⁇ m.
  • the terpene nanosheets have a thickness of 0.3-20 nm.
  • the terpene nanosheet comprises a layer of terpene or a plurality of layers of monoterpenes repeatedly stacked vertically in a plane direction thereof.
  • the terpene nanosheets have a thickness of from 1 to 64 atomic layers. That is, it is formed by stacking 1-64 layers of monolayer terpenes.
  • the thickness of the terpene nanosheet is -19.84 nm.
  • the thickness of the terpene nanosheets is from 0.3 to 15 nm.
  • the terpene nanosheets are formed by stacking 1 to 10 layers of terpenes.
  • the terpene nanosheets have a thickness of 0.3 to 3 nm.
  • the shape of the terpene nanosheets includes, but is not limited to, a square, a circle, a triangle, a polygon, and the like.
  • the terpene nanosheets provided by the invention have a relatively regular shape, uniform size, good dispersibility and less toxicity, and are convenient for use in the fields of preparation of optical, electrical, biological medicine (for example, preparation of photothermal therapeutic drugs, optical labeling drugs) and the like. .
  • SEM scanning electron microscope
  • AFM atomic force microscopy
  • FIG. 4 is a graph showing the ultraviolet-visible-near-infrared absorption spectrum of a terpene nanosheet prepared in an example of the present invention in an NMP solvent.
  • a method for preparing a terpene nanosheet comprising the steps of:
  • the resulting solution was placed in a BILON-1800Y (1800 W maximum power), and the probe was ultrasonicated at 60% power (ie, 1080 W power) for 24 hours at 4 ° C to obtain a first ultrasound. liquid;
  • the first ultrasonic liquid is further placed in a Xinzhi ultrasonic constant temperature cleaning machine SBL-22DT, and subjected to a second water bath ultrasonic vibration at 70% power for 3 hours at a constant temperature of 10 ° C to obtain a second ultrasonic liquid;
  • the second ultrasonic liquid was divided into 4 parts on average, transferred into a 50 mL centrifuge tube, centrifuged at 3000 rpm (5000 g centrifugal force) for 20 minutes using a Hercynian HR20MW centrifuge, and the resulting supernatant was separately transferred to 4 new ones.
  • centrifugation was further carried out at 7000 rpm (11667 g centrifugal force) for 20 minutes, and the intraduct precipitate was collected to obtain the desired terpene nanosheet (about 71.4 mg).
  • a method for preparing a terpene nanosheet comprising the steps of:
  • the solution was placed in a BILON-1800Y (1800 W maximum power), and the probe was ultrasonicated at 75% power (ie, 1350 W) for 15 hours to obtain a first ultrasonic solution;
  • the first ultrasonic liquid is further placed in a Xinzhi ultrasonic constant temperature cleaning machine SBL-22DT, and the second water bath is ultrasonically irradiated for 3 hours at a power of 450 W to obtain a second ultrasonic liquid;
  • FIG. 1 is a scanning electron microscope (SEM) photograph of a terpene nanosheet prepared in accordance with an embodiment of the present invention.
  • SEM scanning electron microscope
  • FIG. 1 there are a large number of distinct flakes, i.e., terpene nanosheets.
  • a magnified layered structure can be seen in a magnified view, indicating that the desired terpene nanosheet can be stripped using the preparation method of the present invention.
  • the terpene nanosheet has a lateral dimension of 100 nm to 10 ⁇ m, and is repeatedly stacked by one or more layers of monoterpene in a plane perpendicular thereto to form a layered feather-like structure, and the thickness of the terpene nanosheet is formed. for -19.84 nm.
  • terpene nanosheet is an analysis result of atomic force microscopy (AFM) of a terpene nanosheet prepared in an example of the present invention.
  • AFM atomic force microscopy
  • FIG 3 is a Raman graph of a terpene nanosheet prepared in accordance with an embodiment of the present invention.
  • the two characteristic peaks of 70 cm -1 and 97 cm -1 are more obvious, which indicates that the preparation method provided by the present invention can be peeled off to form ruthenium. Alkene nanosheets.
  • FIG. 4 is a graph showing the ultraviolet-visible-near-infrared absorption spectrum of a terpene nanosheet prepared in an example of the present invention in an NMP solvent. As can be seen from FIG. 4, the terpene nanosheets provided by the present invention exhibit significant absorption characteristics in the region of 300-1100 nm.
  • Example 1 To highlight the beneficial effects of the present invention, the present invention also sets forth the following comparative examples for Example 1:
  • Comparative Example 1 differs from Example 1 in that, in step (2), probe ultrasound is only used for 24 hours using a ram cell disrupter;
  • Comparative Example 2 differs from Example 1 in that, in step (2), probe ultrasound is first performed using a ram cell disruptor, and then water bath ultrasound is performed;
  • Comparative Example 3 differs from Example 1 in that in step (2), water bath ultrasound is first performed, and probe-type ultrasound is performed, and secondary water bath ultrasound is performed after no probe-type ultrasound.

Abstract

A preparation method for bismuthene nanosheets, comprising: (1) dispersing bismuth powder in an organic solvent to obtain a dispersion liquid; (2) carrying out first ultrasonic water bath treatment on the dispersion liquid, and then carrying out ultrasonic probe treatment to obtain a first ultrasonic liquid; then, carrying out second ultrasonic water bath treatment on the first ultrasonic liquid to obtain a second ultrasonic liquid; (3) carrying out ultra-low-speed centrifugation on the second ultrasonic liquid at 2000-4000 rpm; collecting a supernatant liquid; and then carrying out low-speed centrifugation on the supernatant liquid at 5000-7000 rpm, and collecting precipitates, the precipitates being the bismuthene nanosheets.

Description

一种铋烯纳米片及其制备方法Terpene nanosheet and preparation method thereof
本申请要求于2017年12月26日提交中国专利局、申请号为201711431413.5、发明名称为“一种铋烯纳米片及其制备方法”的中国专利申请的优先权，上述在先申请的内容以引入的方式并入本文本中。The present application claims priority to Chinese Patent Application No. 200911431413.5, entitled "A terpene nanosheet and its preparation method", filed on December 26, 2017, the content of the above-mentioned prior application is The manner of introduction is incorporated into this text.
技术领域Technical field
本发明涉及二维材料领域，特别是涉及一种铋烯纳米片及其制备方法。The invention relates to the field of two-dimensional materials, in particular to a terpene nanosheet and a preparation method thereof.
背景技术Background technique
二维材料，是指电子仅可在两个维度的非纳米尺度(1-100nm)上***(平面运动)的材料，如纳米薄膜。英国曼彻斯特大学两位科学家安德烈·盖姆和克斯特亚·诺沃消洛夫在2004年以胶带法第一次制得石墨烯。此后黑磷(磷烯)、硅烯、锗烯、锑烯、氮化硼、二硫化钼等一系列只有单原子层厚度的准二维材料相继被发现。Two-dimensional materials refer to materials that can move freely (planar motion) on two non-nanoscales (1-100 nm), such as nanofilms. Two scientists, the University of Manchester, Andrei Gem and Kostya Novo, in the UK, made graphene for the first time in 2004 using the tape method. Thereafter, a series of quasi-two-dimensional materials having only a single atomic layer thickness, such as black phosphorus (phosphene), silene, terpene, decene, boron nitride, molybdenum disulfide, etc., have been successively discovered.
铋烯(Bismuthene)是一种由块体金属铋剥离而来的二维材料，具有类似石墨烯的结构。但铋烯为具0.306eV能隙的直接带隙半导体(导带底部和价带顶部在同一位置)，可与光直接耦合，吸收光谱范围较广。此外，由于铋元素的生物相容性强，生物毒性小，故铋烯在光学、电学、生物医药学等方面有着广阔的应用潜力。而二维铋烯片层结构在生物载药、光热、光动力治疗等领域是一种潜在的生物医学基底材料。Bismuthene is a two-dimensional material that is stripped from a bulk metal tantalum and has a graphene-like structure. However, the terpene is a direct bandgap semiconductor with a 0.306 eV energy gap (the bottom of the conduction band and the top of the valence band are at the same position), and can be directly coupled with light, and has a wide absorption spectrum. In addition, due to its high biocompatibility and low biotoxicity, terpene has broad application potential in optics, electricity, biomedicine and other fields. The two-dimensional terpene sheet structure is a potential biomedical base material in the fields of biopharmaceutical, photothermal, photodynamic therapy and the like.
目前，通过机械剥离法(如透明胶带撕分法)、化学气相沉积法等技术来制备片层铋烯材料。但是，机械剥离法制备的片状铋烯材料的产率较低，不适 合商业化生产，且操作繁琐、耗时长；而化学气相沉积法制备的铋烯的量较少，且不易重复。At present, a sheet of terpene material is prepared by a mechanical peeling method (such as a transparent tape tearing method), a chemical vapor deposition method, or the like. However, the sheet-like terpene material prepared by the mechanical exfoliation method has a low yield, is not suitable for commercial production, and is cumbersome and time consuming to operate; and the amount of terpene prepared by chemical vapor deposition is small and difficult to repeat.
发明内容Summary of the invention
鉴于此，本发明提供了一种铋烯纳米片及其制备方法，该制备方法通过将探针超声和水浴超声相结合，通过协同作用以实现对铋粉的剥离，获得单分散性好、尺寸均一的铋烯纳米片。该方法的工艺简单易操作，重现性好、铋烯纳米片的产量或产率较高，易实现低成本产业化生产。In view of this, the present invention provides a terpene nanosheet and a preparation method thereof, which combines ultrasonication of a probe with ultrasonication of a water bath to achieve separation of tantalum powder by synergistic action, and obtains good monodispersity and size. Uniform terpene nanosheets. The method has the advantages of simple and easy operation, good reproducibility, high yield or yield of the terpene nanosheets, and easy realization of low-cost industrial production.
第一方面，本发明提供了一种铋烯纳米片的制备方法，包括以下步骤：In a first aspect, the present invention provides a method for preparing a terpene nanosheet, comprising the steps of:
(1)将铋粉分散在有机溶剂中，得到分散液；其中，铋粉在分散液的浓度为0.5-10mg/mL；(1) dispersing the tantalum powder in an organic solvent to obtain a dispersion; wherein the concentration of the tantalum powder in the dispersion is 0.5-10 mg/mL;
(2)先对所述分散液进行第一次水浴超声，所述第一次水浴超声的功率为400-600W，时间为1-6小时；再在功率为1080-1800W下进行探头式超声10-24小时，得到第一超声液；(2) first performing the first bath ultrasonic wave on the dispersion, the first water bath ultrasonic power is 400-600 W, the time is 1-6 hours; and the probe ultrasonic 10 is performed at a power of 1080-1800 W. - 24 hours, obtaining a first ultrasonic solution;
然后对所述第一超声液进行第二次水浴超声，得到第二超声液；其中，所述第二次水浴超声的功率为400-600W；Then performing a second water bath sonication on the first ultrasonic liquid to obtain a second ultrasonic liquid; wherein the power of the second water bath ultrasonic is 400-600 W;
(3)对所述第二超声液在2000-4000rpm下进行超低速离心，收集上清液，然后对所述上清液在5000-7000rpm下进行低速离心，收集沉淀，所得沉淀即为铋烯纳米片。(3) ultra-low-speed centrifugation of the second ultrasonic solution at 2000-4000 rpm, collecting the supernatant, and then performing low-speed centrifugation on the supernatant at 5000-7000 rpm to collect the precipitate, and the obtained precipitate is terpene. Nanosheets.
可选地，所述有机溶剂包括N-甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、丙酮、四氢呋喃、无水乙醇、甲醇、异丙醇、三氯甲烷和二氯甲烷中的一种或多种，但不限于此。所用有机溶剂的表面能与二维层状铋烯材料的表面能相匹配，二者之间存在一定的相互作用平衡了剥离铋粉所 需要的能量。Optionally, the organic solvent comprises N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, tetrahydrofuran, absolute ethanol, methanol, isopropanol, One or more of chloroform and dichloromethane, but is not limited thereto. The surface energy of the organic solvent used matches the surface energy of the two-dimensional layered terpene material, and there is a certain interaction between the two to balance the energy required to remove the tantalum powder.
可选地，所述铋粉的粒径不超过75μm。例如55-70μm、1-50μm、2-45μm或1-4μm。进一步可选地，所述铋粉的粒径不超过50μm。Optionally, the tantalum powder has a particle size of no more than 75 μm. For example, 55-70 μm, 1-50 μm, 2-45 μm or 1-4 μm. Further optionally, the particle size of the tantalum powder does not exceed 50 μm.
本发明实施例中，所述第一次水浴超声的功率可以为400W、450W、500W、550W、580W或600W。可选地，所述第一次水浴超声的功率为420-600W。In the embodiment of the present invention, the power of the first water bath ultrasound may be 400W, 450W, 500W, 550W, 580W or 600W. Optionally, the power of the first water bath ultrasound is 420-600W.
可选地，所述第二次水浴超声的时间为1-6小时。进一步可选为1-3小时。Optionally, the second bath is sonicated for a period of from 1 to 6 hours. Further optional is 1-3 hours.
其中，所述第二次水浴超声的功率可以为400W、450W、500W、550W、580W或600W。可选地，所述第二次水浴超声的功率为420-600W。所述第二次水浴超声的功率或时间可以与所述第一次水浴超声的功率或时间相同或不同。Wherein, the power of the second water bath ultrasound may be 400W, 450W, 500W, 550W, 580W or 600W. Optionally, the power of the second water bath ultrasound is 420-600W. The power or time of the second water bath ultrasound may be the same or different than the power or time of the first water bath ultrasound.
本发明实施例中，所述探针式超声的功率可以为1100W、1200W、1300W、1400W、1500W、1600W或1700W。可选地，所述探头式超声的功率为1200-1700W。In the embodiment of the present invention, the power of the probe-type ultrasound may be 1100W, 1200W, 1300W, 1400W, 1500W, 1600W or 1700W. Optionally, the probe-type ultrasound has a power of 1200-1700W.
本发明实施例中，所述探针式超声的时间可以为10h、12h、15h、20h或24h。可选地，所述探头式超声的时间为12-24小时。In the embodiment of the present invention, the time of the probe-type ultrasound may be 10h, 12h, 15h, 20h or 24h. Optionally, the time of the probe-type ultrasound is 12-24 hours.
可选地，所述探针式超声是在温度不超过10℃的冰浴条件中进行。优选地，所述探针式超声时的温度为0-10℃，进一步优选为4-10℃。所述冰浴条件，是指在所述探针式超声过程中，将装有待超声的溶液的容器置于装有冰块的另一容器(如烧杯、试管)中。Alternatively, the probe-type ultrasound is performed in an ice bath condition at a temperature not exceeding 10 °C. Preferably, the temperature at the time of the probe-type ultrasonic wave is 0 to 10 ° C, and more preferably 4 to 10 ° C. The ice bath condition means that the container containing the solution to be ultrasonicated is placed in another container (such as a beaker, a test tube) containing ice cubes during the probe-type ultrasonic process.
可选地，所述第一次水浴超声是在温度为5-10℃下进行。Optionally, the first water bath sonication is performed at a temperature of 5-10 °C.
可选地，所述第二次水浴超声是在温度为5-10℃下进行。Optionally, the second water bath sonication is carried out at a temperature of 5-10 °C.
可选地，所述超低速离心的离心时间为15-30min。例如为12、15、20、 25或30min。Optionally, the ultra-low speed centrifugation has a centrifugation time of 15-30 min. For example, 12, 15, 20, 25 or 30 min.
可选地，所述超低速离心的转速为2000-3000rpm。Optionally, the ultra low speed centrifugation speed is 2000-3000 rpm.
可选地，所述低速离心的离心时间为15-30min。例如为12、15、20、25或30min。Optionally, the centrifugation time of the low speed centrifugation is 15-30 min. For example, 12, 15, 20, 25 or 30 min.
可选地，所述低速离心的转速为6000-7000rpm。Optionally, the low speed centrifugation speed is 6000-7000 rpm.
所述低速离心后得到的沉淀(即铋烯纳米片)可以再分散到第二溶剂中，得到含铋烯纳米片的溶液。可选地，所述第二溶剂包括N-甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、丙酮、四氢呋喃、无水乙醇、甲醇和异丙醇中的一种或多种。The precipitate obtained after the low-speed centrifugation (i.e., the terpene nanosheet) can be redispersed into the second solvent to obtain a solution containing the terpene nanosheet. Optionally, the second solvent comprises N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, tetrahydrofuran, absolute ethanol, methanol and isopropanol. One or more of them.
本发明中，对铋粉分散液的第一次水浴超声是通过超声空泡效应将铋粉初步打碎，使其部分溶入有机溶剂中，可避免直接采用探头式超声对探头式超声仪的损耗，延长超声时间；接下来的探针式超声是将初步打碎的铋粉大量地打碎、剥离成片层结构的铋烯，使其大量溶入有机溶剂中；最后的第二次水浴超声可将剥离后的铋烯层状材料进一步打碎成更小的颗粒，得到铋烯纳米片，且进一步保证不会团聚，以便后续进行离心纯化处理。In the present invention, the first water bath ultrasonic wave of the bismuth powder dispersion liquid is initially broken by the ultrasonic vacuolar effect, and partially dissolved into the organic solvent, thereby avoiding direct use of the probe type ultrasonic on the probe type ultrasonic system. Loss, prolong the ultrasonic time; the next probe-type ultrasound is to break up the initially broken strontium powder and peel it into a layer structure of decene, so that it is dissolved in organic solvent; the last second water bath Ultrasound can further break up the exfoliated terpene layered material into smaller particles to obtain a terpene nanosheet, and further ensure that it does not agglomerate for subsequent centrifugal purification treatment.
本发明第一方面提供的铋烯纳米片的制备方法，将探针超声和水浴超声相结合的液相剥离法，通过协同作用以实现对铋粉的剥离，此方法工艺简单易操作，产率较高，相比目前的机械剥离法及化学气相沉积法等有明显的优势，可获得尺寸可控的单分散性好的铋烯纳米片，易实现低成本产业化生产。这为铋烯纳米片在生物医学领域中的应用奠定基础。The method for preparing a terpene nanosheet provided by the first aspect of the invention, the liquid phase stripping method combining probe ultrasonic and water bath ultrasonic, synergistically to achieve stripping of tantalum powder, the method is simple and easy to operate, and the yield is Higher, compared with the current mechanical stripping method and chemical vapor deposition method, it has obvious advantages, and can obtain a monodisperse terpene nanosheet with controllable size and easy to realize low-cost industrial production. This lays the foundation for the application of terpene nanosheets in the biomedical field.
第二方面，本发明还提供了由上述制备方法制备得到的铋烯纳米片。所述铋烯纳米片的厚度在20nm以下，所述铋烯纳米片的横向尺寸为100nm～10μm。 其中，横向尺寸是指铋烯纳米片的长度或宽度。In a second aspect, the present invention also provides a terpene nanosheet prepared by the above preparation method. The terpene nanosheet has a thickness of 20 nm or less, and the terpene nanosheet has a lateral dimension of 100 nm to 10 μm. Wherein, the lateral dimension refers to the length or width of the terpene nanosheet.
可选地，所述铋烯纳米片的横向尺寸为200nm～10μm。例如为300nm、500nm、800nm、1μm、2μm、5μm、8μm或10μm。Optionally, the terpene nanosheet has a lateral dimension of 200 nm to 10 μm. For example, it is 300 nm, 500 nm, 800 nm, 1 μm, 2 μm, 5 μm, 8 μm or 10 μm.
可选地，所述铋烯纳米片的横向尺寸为500nm～10μm。Optionally, the terpene nanosheet has a lateral dimension of 500 nm to 10 μm.
可选地，所述铋烯纳米片的横向尺寸为1μm～10μm。Optionally, the terpene nanosheets have a lateral dimension of from 1 μm to 10 μm.
可选地，所述铋烯纳米片的厚度为0.3-20nm。Optionally, the terpene nanosheets have a thickness of 0.3-20 nm.
其中，所述铋烯纳米片包括一层铋烯或多层的单层铋烯在垂直其平面方向上重复堆叠而成。Wherein, the terpene nanosheet comprises a layer of terpene or a plurality of layers of monoterpenes repeatedly stacked vertically in a plane direction thereof.
可选地，所述铋烯纳米片为1～64个原子层厚度。即，由1-64层的单层铋烯堆叠而成。所述铋烯纳米片的厚度为
Figure PCTCN2018099566-appb-000001
-19.84nm。 Optionally, the terpene nanosheets have a thickness of from 1 to 64 atomic layers. That is, it is formed by stacking 1-64 layers of monolayer terpenes. The thickness of the terpene nanosheet is
Figure PCTCN2018099566-appb-000001
-19.84 nm.
进一步可选地，所述铋烯纳米片的厚度为0.3-15nm。Further optionally, the thickness of the terpene nanosheets is from 0.3 to 15 nm.
可选地，所述铋烯纳米片为1～10层的铋烯堆叠而成。所述铋烯纳米片的厚度为0.3-3nm。Optionally, the terpene nanosheets are formed by stacking 1 to 10 layers of terpenes. The terpene nanosheets have a thickness of 0.3 to 3 nm.
可选地，所述铋烯纳米片的形状包括但不限于方形、圆形、三角形、多边形等形状。Optionally, the shape of the terpene nanosheets includes, but is not limited to, a square, a circle, a triangle, a polygon, and the like.
本发明提供的铋烯纳米片的形状较为规整、尺寸较均一，分散性较好，毒性较小，便于用于制备光学、电学、生物医药(例如制备光热治疗药物、光学标记药物)等领域。The terpene nanosheets provided by the invention have a relatively regular shape, uniform size, good dispersibility and less toxicity, and are convenient for use in the fields of preparation of optical, electrical, biological medicine (for example, preparation of photothermal therapeutic drugs, optical labeling drugs) and the like. .
本发明实施例的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。The advantages of the embodiments of the present invention will be set forth in part in the description which follows.
附图说明DRAWINGS
图1为本发明实施例制得的铋烯纳米片的扫描电子显微镜(SEM)照片；1 is a scanning electron microscope (SEM) photograph of a terpene nanosheet prepared according to an embodiment of the present invention;
图2为本发明实施例制得的铋烯纳米片的原子力显微镜(AFM)的分析结果；2 is an analysis result of atomic force microscopy (AFM) of a terpene nanosheet prepared according to an embodiment of the present invention;
图3为本发明实施例制得的铋烯纳米片的拉曼谱图；3 is a Raman spectrum of a terpene nanosheet prepared according to an embodiment of the present invention;
图4为本发明实施例制得的铋烯纳米片在NMP溶剂中的紫外-可见-近红外吸收光谱图。4 is a graph showing the ultraviolet-visible-near-infrared absorption spectrum of a terpene nanosheet prepared in an example of the present invention in an NMP solvent.
具体实施方式Detailed ways
以下所述是本发明实施例的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。The following are the preferred embodiments of the embodiments of the present invention, and it should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the embodiments of the present invention. And retouching is also considered to be the scope of protection of the embodiments of the present invention.
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不变主权利的范围内，可以适当的进行变更实施。The embodiments of the present invention are further described below in various embodiments. The embodiments of the present invention are not limited to the specific embodiments below. Changes can be implemented as appropriate within the scope of the invariable primary rights.
实施例1Example 1
一种铋烯纳米片的制备方法，包括以下步骤：A method for preparing a terpene nanosheet, comprising the steps of:
(1)取一个250mL容量的蜀牛玻璃瓶，装入120mL的NMP溶剂，再加入120mg的200目(200粒/每平方英寸，也即粒径为0.074mm)铋粉，得到铋粉初始浓度为1mg/mL(或称为1000ppm)的分散液；(1) Take a 250mL yak glass bottle, add 120mL of NMP solvent, and then add 120mg of 200 mesh (200 particles / square inch, that is, particle size of 0.074mm) bismuth powder to obtain the initial concentration of bismuth powder. a dispersion of 1 mg/mL (or 1000 ppm);
(2)将(1)中玻璃瓶置入新芝超声波恒温清洗机SBL-22DT中，在10℃恒温下以最大功率(600W)的70％(即以420W的功率)进行水浴超声3小时；(2) Put the glass bottle in (1) into the Xinzhi ultrasonic constant temperature cleaning machine SBL-22DT, and perform ultrasonic bathing for 3 hours at 70% (maximum power (600W)) of the maximum power (600W) at a constant temperature of 10 °C;
水浴超声之后，再将所得溶液置于比朗细胞破碎仪BILON-1800Y内(1800W最大功率)，在4℃下，以60％功率(即1080W的功率)进行探头 超声24小时，得到第一超声液；After ultrasonic bathing, the resulting solution was placed in a BILON-1800Y (1800 W maximum power), and the probe was ultrasonicated at 60% power (ie, 1080 W power) for 24 hours at 4 ° C to obtain a first ultrasound. liquid;
然后对所述第一超声液再置入新芝超声波恒温清洗机SBL-22DT中，在10℃恒温下以70％功率进行第二次水浴超声3小时，得到第二超声液；Then, the first ultrasonic liquid is further placed in a Xinzhi ultrasonic constant temperature cleaning machine SBL-22DT, and subjected to a second water bath ultrasonic vibration at 70% power for 3 hours at a constant temperature of 10 ° C to obtain a second ultrasonic liquid;
(3)对所述第二超声液平均分为4份，移入50mL离心管，采用赫西HR20MW离心机在3000rpm转速下(5000g离心力)进行离心20分钟，将所得上清液分别移入4个新的50mL离心管中，再于7000rpm转速下(11667g离心力)进行离心20分钟，收集管内沉淀，即为所需的铋烯纳米片(约71.4mg)。(3) The second ultrasonic liquid was divided into 4 parts on average, transferred into a 50 mL centrifuge tube, centrifuged at 3000 rpm (5000 g centrifugal force) for 20 minutes using a Hercynian HR20MW centrifuge, and the resulting supernatant was separately transferred to 4 new ones. In a 50 mL centrifuge tube, centrifugation was further carried out at 7000 rpm (11667 g centrifugal force) for 20 minutes, and the intraduct precipitate was collected to obtain the desired terpene nanosheet (about 71.4 mg).
经计算可得，本发明实施例1中，所述铋烯纳米片的产率为71.4mg/120mg＝59.5％。It can be calculated that in the first embodiment of the present invention, the yield of the terpene nanosheet is 71.4 mg / 120 mg = 59.5%.
实施例2Example 2
一种铋烯纳米片的制备方法，包括以下步骤：A method for preparing a terpene nanosheet, comprising the steps of:
(1)取一个500mL容量的蜀牛玻璃瓶，装入400mL的NMP溶剂，再加入200mg的300目铋粉，得到铋粉初始浓度为0.5mg/mL的分散液；(1) taking a 500 mL capacity yak glass bottle, charging 400 mL of NMP solvent, and then adding 200 mg of 300 mesh mash powder to obtain a dispersion having an initial concentration of bismuth powder of 0.5 mg/mL;
(2)将(1)中玻璃瓶置入新芝超声波恒温清洗机SBL-22DT中，在4℃恒温下以480W的功率进行水浴超声2小时；(2) Put the glass bottle in (1) into the Xinzhi ultrasonic constant temperature cleaning machine SBL-22DT, and perform ultrasonic bathing at 480W for 2 hours at a constant temperature of 4 °C;
水浴超声之后，再将所得溶液置于比朗细胞破碎仪BILON-1800Y内(1800W最大功率)，以75％功率(即1350W的功率)进行探头超声15小时，得到第一超声液；After ultrasonic bathing, the solution was placed in a BILON-1800Y (1800 W maximum power), and the probe was ultrasonicated at 75% power (ie, 1350 W) for 15 hours to obtain a first ultrasonic solution;
然后对所述第一超声液再置入新芝超声波恒温清洗机SBL-22DT中，以450W的功率进行第二次水浴超声3小时，得到第二超声液；Then, the first ultrasonic liquid is further placed in a Xinzhi ultrasonic constant temperature cleaning machine SBL-22DT, and the second water bath is ultrasonically irradiated for 3 hours at a power of 450 W to obtain a second ultrasonic liquid;
(3)对所述第二超声液平均分为4份，移入50mL离心管，采用赫西 HR20MW离心机在2000rpm转速下离心30分钟，将所得上清液分别移入4个新的50mL离心管中，再于6500rpm转速下离心25分钟，收集管内沉淀，即为所需的铋烯纳米片(产率为65％)。(3) The second ultrasonic solution was divided into 4 portions, transferred into a 50 mL centrifuge tube, centrifuged at 2000 rpm for 30 minutes using a Hercynian HR20MW centrifuge, and the resulting supernatant was separately transferred into 4 new 50 mL centrifuge tubes. After centrifugation at 6500 rpm for 25 minutes, the in-tube precipitate was collected to obtain the desired terpene nanosheets (yield 65%).
图1为本发明实施例制得的铋烯纳米片的扫描电子显微镜(SEM)照片。从图1中可看出，图中存在大量明显的片状物质，即铋烯纳米片。放大看可见明显的层状结构，说明采用本发明的制备方法可以剥出所需的铋烯纳米片。所述铋烯纳米片的横向尺寸在100nm～10μm，由一层或多层的单层铋烯在垂直其平面方向上重复堆叠形成层状羽毛样结构，形成的所述铋烯纳米片的厚度为
Figure PCTCN2018099566-appb-000002
-19.84nm。 1 is a scanning electron microscope (SEM) photograph of a terpene nanosheet prepared in accordance with an embodiment of the present invention. As can be seen from Figure 1, there are a large number of distinct flakes, i.e., terpene nanosheets. A magnified layered structure can be seen in a magnified view, indicating that the desired terpene nanosheet can be stripped using the preparation method of the present invention. The terpene nanosheet has a lateral dimension of 100 nm to 10 μm, and is repeatedly stacked by one or more layers of monoterpene in a plane perpendicular thereto to form a layered feather-like structure, and the thickness of the terpene nanosheet is formed. for
Figure PCTCN2018099566-appb-000002
-19.84 nm.
图2为本发明实施例制得的铋烯纳米片的原子力显微镜(AFM)的分析结果。图内存在大量厚度为3nm(ΔZ)的片状结构，说明本发明提供的制备方法可成功剥离形成铋烯纳米片，所述铋烯纳米片约由10层单层铋烯堆叠而成，即，所述铋烯纳米片为10个铋原子层厚度。2 is an analysis result of atomic force microscopy (AFM) of a terpene nanosheet prepared in an example of the present invention. There are a large number of sheet-like structures with a thickness of 3 nm (ΔZ), indicating that the preparation method provided by the present invention can be successfully stripped to form a terpene nanosheet, which is composed of 10 layers of monolayers of terpenes, that is, The terpene nanosheets have a thickness of 10 germanium atom layers.
图3为本发明实施例制得的铋烯纳米片的拉曼曲线图。在1064nm的激发波长下，70cm -1和97cm -1(分别对应于Bi元素的E g和A 1g振动模)这两个特征峰都较为明显，这说明本发明提供的制备方法可剥离形成铋烯纳米片。 3 is a Raman graph of a terpene nanosheet prepared in accordance with an embodiment of the present invention. At the excitation wavelength of 1064 nm, the two characteristic peaks of 70 cm -1 and 97 cm -1 (corresponding to the E g and A 1g vibration modes of the Bi element, respectively) are more obvious, which indicates that the preparation method provided by the present invention can be peeled off to form ruthenium. Alkene nanosheets.
图4为本发明实施例制得的铋烯纳米片在NMP溶剂中的紫外-可见-近红外吸收光谱图。由图4可见，本发明提供的铋烯纳米片在300-1100nm区域均表现出明显的吸收特性。4 is a graph showing the ultraviolet-visible-near-infrared absorption spectrum of a terpene nanosheet prepared in an example of the present invention in an NMP solvent. As can be seen from FIG. 4, the terpene nanosheets provided by the present invention exhibit significant absorption characteristics in the region of 300-1100 nm.
为突出本发明的有益效果，本发明还针对实施例1设置以下对比实施例：To highlight the beneficial effects of the present invention, the present invention also sets forth the following comparative examples for Example 1:
对比例1与实施例1的区别在于：步骤(2)中，只采用比朗细胞破碎仪 进行探头超声24小时；Comparative Example 1 differs from Example 1 in that, in step (2), probe ultrasound is only used for 24 hours using a ram cell disrupter;
对比例2与实施例1的区别在于：步骤(2)中，先采用比朗细胞破碎仪进行探头超声，再进行水浴超声；Comparative Example 2 differs from Example 1 in that, in step (2), probe ultrasound is first performed using a ram cell disruptor, and then water bath ultrasound is performed;
对比例3与实施例1的区别在于：步骤(2)中，先进行水浴超声，再进行探头式超声，而没有再探头式超声之后再进行二次水浴超声。Comparative Example 3 differs from Example 1 in that in step (2), water bath ultrasound is first performed, and probe-type ultrasound is performed, and secondary water bath ultrasound is performed after no probe-type ultrasound.
结果发现：turn out:
对比例1制得的产品与实施例1的铋烯纳米片相比，其横向尺寸主要在1μm以上，所述铋烯纳米片的产率为63.9mg/120mg＝53.25％。The product prepared in Comparative Example 1 had a lateral dimension of mainly 1 μm or more as compared with the terpene nanosheet of Example 1, and the yield of the terpene nanosheet was 63.9 mg / 120 mg = 53.25%.
对比例2制得的产品与实施例1相比，铋烯纳米片的产率为67.8mg/120mg＝56.5％。其中，也含有不少横向尺寸在1μm以上的纳米片。The product obtained in Comparative Example 2 had a yield of the terpene nanosheet of 67.8 mg / 120 mg = 56.5% as compared with Example 1. Among them, there are also a lot of nanosheets having a lateral size of 1 μm or more.
对比例3制得的产品与实施例1相比，所述铋烯纳米片的产率为68.2mg/120mg＝56.83％。且对比例3的产品在分散在有机溶剂中，静置6小时后会有微量团聚现象。The product obtained in Comparative Example 3 had a yield of the terpene nanosheet of 68.2 mg / 120 mg = 56.83% as compared with Example 1. Moreover, the product of Comparative Example 3 was dispersed in an organic solvent, and a slight agglomeration occurred after standing for 6 hours.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (19)

  1. 一种铋烯纳米片的制备方法，其特征在于，包括以下步骤：A method for preparing a terpene nanosheet, comprising the steps of:
    (1)将铋粉分散在有机溶剂中，得到分散液；其中，铋粉在分散液的浓度为0.5-10mg/mL；(1) dispersing the tantalum powder in an organic solvent to obtain a dispersion; wherein the concentration of the tantalum powder in the dispersion is 0.5-10 mg/mL;
    (2)先对所述分散液进行第一次水浴超声，所述第一次水浴超声的功率为400-600W，时间为1-6小时；再在功率为1080-1800W下进行探头式超声10-24小时，得到第一超声液；(2) first performing the first bath ultrasonic wave on the dispersion, the first water bath ultrasonic power is 400-600 W, the time is 1-6 hours; and the probe ultrasonic 10 is performed at a power of 1080-1800 W. - 24 hours, obtaining a first ultrasonic solution;
    然后对所述第一超声液进行第二次水浴超声，得到第二超声液；其中，所述第二次水浴超声的功率为400-600W；Then performing a second water bath sonication on the first ultrasonic liquid to obtain a second ultrasonic liquid; wherein the power of the second water bath ultrasonic is 400-600 W;
    (3)对所述第二超声液在2000-4000rpm下进行超低速离心，收集上清液，然后对所述上清液在5000-7000rpm下进行低速离心，收集沉淀，所得沉淀即为铋烯纳米片。(3) ultra-low-speed centrifugation of the second ultrasonic solution at 2000-4000 rpm, collecting the supernatant, and then performing low-speed centrifugation on the supernatant at 5000-7000 rpm to collect the precipitate, and the obtained precipitate is terpene. Nanosheets.
  2. 如权利要求1所述的制备方法，其特征在于，所述铋粉的粒径不超过75μm。The preparation method according to claim 1, wherein the niobium powder has a particle diameter of not more than 75 μm.
  3. 如权利要求1所述的制备方法，其特征在于，所述有机溶剂包括N-甲基吡咯烷酮、二甲基甲酰胺、二甲基亚砜、丙酮、四氢呋喃、无水乙醇、甲醇、异丙醇、三氯甲烷和二氯甲烷中的一种或多种。The preparation method according to claim 1, wherein the organic solvent comprises N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, absolute ethanol, methanol, isopropanol. One or more of chloroform and dichloromethane.
  4. 如权利要求1所述的制备方法，其特征在于，所述第一次水浴超声的功率为420-600W。The preparation method according to claim 1, wherein the first water bath ultrasonic power is 420-600 W.
  5. 如权利要求1所述的制备方法，其特征在于，所述第二次水浴超声的功率为420-600W；所述第二次水浴超声的时间为1-6小时。The preparation method according to claim 1, wherein the power of the second water bath ultrasonic is 420-600 W; and the time of the second water bath ultrasonic is 1-6 hours.
  6. 如权利要求1所述的制备方法，其特征在于，所述第一次水浴超声和 所述第二次水浴超声分别是在温度为5-10℃下进行。The preparation method according to claim 1, wherein said first water bath sonication and said second water bath ultrasonic wave are each performed at a temperature of 5 to 10 °C.
  7. 如权利要求1所述的制备方法，其特征在于，所述探头式超声的功率为1200-1700W。The preparation method according to claim 1, wherein the probe type ultrasonic power is 1200-1700 W.
  8. 如权利要求1所述的制备方法，其特征在于，所述探针式超声是在温度不超过10℃的冰浴条件中进行。The preparation method according to claim 1, wherein the probe-type ultrasonication is carried out in an ice bath condition at a temperature not exceeding 10 °C.
  9. 如权利要求1所述的制备方法，其特征在于，所述超低速离心的转速为2000-3000rpm；所述超低速离心的离心时间为15-30min。The preparation method according to claim 1, wherein the ultra low speed centrifugation has a rotational speed of 2000 to 3000 rpm; and the ultra low speed centrifugation has a centrifugal time of 15 to 30 min.
  10. 如权利要求1所述的制备方法，其特征在于，所述低速离心的转速为6000-7000rpm。The preparation method according to claim 1, wherein the low-speed centrifugal rotation speed is 6000-7000 rpm.
  11. 一种铋烯纳米片，其特征在于，所述铋烯纳米片的厚度在20nm以下，所述铋烯纳米片的横向尺寸为100nm～10μm。A terpene nanosheet characterized in that the thickness of the terpene nanosheet is 20 nm or less, and the transverse dimension of the terpene nanosheet is 100 nm to 10 μm.
  12. 如权利要求11所述的铋烯纳米片，其特征在于，所述铋烯纳米片的横向尺寸为200nm～10μm。The terpene nanosheet according to claim 11, wherein the terpene nanosheet has a lateral dimension of from 200 nm to 10 μm.
  13. 如权利要求11所述的铋烯纳米片，其特征在于，所述铋烯纳米片的横向尺寸为500nm～10μm。The terpene nanosheet according to claim 11, wherein the terpene nanosheet has a lateral dimension of from 500 nm to 10 μm.
  14. 如权利要求11所述的铋烯纳米片，其特征在于，所述铋烯纳米片的横向尺寸为1μm～10μm。The terpene nanosheet according to claim 11, wherein the terpene nanosheet has a lateral dimension of from 1 μm to 10 μm.
  15. 如权利要求11所述的铋烯纳米片，其特征在于，所述铋烯纳米片包括1-64层的单层铋烯堆叠而成。The terpene nanosheet of claim 11, wherein the terpene nanosheet comprises a stack of 1-44 layers of monolayers of terpenes.
  16. 如权利要求11所述的铋烯纳米片，其特征在于，所述铋烯纳米片的厚度为0.3-15nm。The terpene nanosheet of claim 11, wherein the terpene nanosheet has a thickness of from 0.3 to 15 nm.
  17. 如权利要求15所述的铋烯纳米片，其特征在于，所述铋烯纳米片由 1-10层的单层铋烯堆叠而成，其厚度为0.3-3nm。The terpene nanosheet according to claim 15, wherein the terpene nanosheet is composed of 1-10 layers of a single layer of decene and has a thickness of 0.3 to 3 nm.
  18. 如权利要求11所述的铋烯纳米片，其特征在于，所述铋烯纳米片的形状包括方形、圆形、三角形和多边形中的一种或多种。The terpene nanosheet of claim 11, wherein the shape of the terpene nanosheet comprises one or more of a square, a circle, a triangle, and a polygon.
  19. 如权利要求11-18任一项所述的铋烯纳米片，其特征在于，所述铋烯纳米片由权利要求1-10任一项所述的制备方法制得。The terpene nanosheet according to any one of claims 11 to 18, wherein the terpene nanosheet is produced by the production method according to any one of claims 1 to 10.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112618715A (en) * 2021-01-06 2021-04-09 浙江理工大学 Preparation method of drug-loaded photothermal photodynamic nanoparticles based on electrostatic adsorption
WO2023224579A1 (en) * 2022-05-20 2023-11-23 Koc Universitesi Bismuthene as a versatile photocatalyst operating under variable conditions for the photoredox c–h bond functionalization

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108284220B (en) * 2017-12-26 2021-01-05 深圳大学 Bismuth-alkene nanosheet and preparation method thereof
US11623873B2 (en) * 2018-12-06 2023-04-11 Purdue Research Foundation Substrate-free crystalline 2D bismuthene
CN112792350B (en) * 2019-10-25 2022-04-19 中国科学院福建物质结构研究所 Antimony and/or bismuth nanosheet, stibene and/or bislimonene and preparation method and application thereof
CN110982900B (en) * 2019-12-13 2023-10-03 深圳瀚光科技有限公司 Biosensor based on bismuth alkene nanosheet fluorescence quenching, miRNA detection kit and application
CN111790904A (en) * 2020-05-25 2020-10-20 南京理工大学 Method for preparing bismuth-alkene nanosheets by liquid-phase laser irradiation method
CN112846199B (en) * 2021-01-08 2022-09-09 新乡医学院 Method for preparing ultrathin bismuth-alkene nanosheets by heating, freezing, grinding and ultrasonic
CN114147211B (en) * 2021-12-07 2024-01-30 合肥工业大学 Copper-tin bimetal alkene nanosheet and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030224168A1 (en) * 2002-05-30 2003-12-04 The Regents Of The University Of California Chemical manufacture of nanostructured materials
CN104591181A (en) * 2015-02-13 2015-05-06 山东大学 Method for preparing two-dimensional composite material by utilizing nanosheet layer peeling
CN107275628A (en) * 2017-07-19 2017-10-20 华中科技大学 The preparation method and lithium ion battery of a kind of two-dimentional bismuth alkene
CN108284220A (en) * 2017-12-26 2018-07-17 深圳大学 A kind of bismuth alkene nanometer sheet and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102674476A (en) * 2012-05-17 2012-09-19 哈尔滨工业大学 Chemical preparation method of magnetic graphene
US9108275B2 (en) * 2012-10-10 2015-08-18 Federal-Mogul Corporation Bi-material strip and a method of bonding strips of different materials together
CN104843695A (en) * 2015-05-26 2015-08-19 山东大学 Method for preparing two-dimensional nanosheet material through all-directional ultrasonic agitation process
CN105600760B (en) * 2015-12-25 2018-01-23 湖北中科墨磷科技有限公司 A kind of small size black phosphorus piece and preparation method thereof
CN106335885B (en) * 2016-08-17 2017-10-03 深圳先进技术研究院 A kind of black phosphorus nanometer sheet and preparation method and application
CN107234244B (en) * 2017-06-23 2019-10-18 南京理工大学 A kind of ultrasonic liquid-phase strip preparation method of big yield antimony alkene quantum dot

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030224168A1 (en) * 2002-05-30 2003-12-04 The Regents Of The University Of California Chemical manufacture of nanostructured materials
CN104591181A (en) * 2015-02-13 2015-05-06 山东大学 Method for preparing two-dimensional composite material by utilizing nanosheet layer peeling
CN107275628A (en) * 2017-07-19 2017-10-20 华中科技大学 The preparation method and lithium ion battery of a kind of two-dimentional bismuth alkene
CN108284220A (en) * 2017-12-26 2018-07-17 深圳大学 A kind of bismuth alkene nanometer sheet and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112618715A (en) * 2021-01-06 2021-04-09 浙江理工大学 Preparation method of drug-loaded photothermal photodynamic nanoparticles based on electrostatic adsorption
CN112618715B (en) * 2021-01-06 2023-03-14 浙江理工大学 Preparation method of drug-loaded photothermal photodynamic nanoparticles based on electrostatic adsorption
WO2023224579A1 (en) * 2022-05-20 2023-11-23 Koc Universitesi Bismuthene as a versatile photocatalyst operating under variable conditions for the photoredox c–h bond functionalization

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