WO2020262035A1 - Procédé de production d'une composition contenant du phosphore noir, et composition contenant du phosphore noir - Google Patents

Procédé de production d'une composition contenant du phosphore noir, et composition contenant du phosphore noir Download PDF

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WO2020262035A1
WO2020262035A1 PCT/JP2020/023168 JP2020023168W WO2020262035A1 WO 2020262035 A1 WO2020262035 A1 WO 2020262035A1 JP 2020023168 W JP2020023168 W JP 2020023168W WO 2020262035 A1 WO2020262035 A1 WO 2020262035A1
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black phosphorus
phosphorus
containing composition
black
composition
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PCT/JP2020/023168
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Japanese (ja)
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晃代 小澤
幸浩 国吉
朋子 吉田
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堺化学工業株式会社
公立大学法人大阪
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    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a black phosphorus-containing composition and a black phosphorus-containing composition. More specifically, the present invention relates to a method for producing a black phosphorus-containing composition useful for a battery material, a photocatalytic material, a thermoelectric conversion material, a photodetector sensor, a field effect transistor, and the like, and a black phosphorus-containing composition.
  • Black phosphorus is one of the allotropes of phosphorus and is known as an elemental semiconductor.
  • Black phosphorus like graphene, has a layered structure and has a bandgap as opposed to graphene, which does not have a bandgap.
  • black phosphorus has a wide range of absorption in the ultraviolet, visible, and near-infrared light regions, and is therefore expected to be used in various applications. Specifically, its use in photocatalytic materials for producing hydrogen and hydrocarbons, battery materials such as anodes of lithium ion batteries, thermoelectric conversion materials, light detection sensors, field effect transistors, and the like is being studied.
  • Non-Patent Documents 1 and 2 disclose a method for treating red phosphorus at a high temperature and high pressure.
  • Non-Patent Document 3 discloses a flux method in which red phosphorus is heated in tin iodide under vacuum.
  • Non-Patent Document 4 discloses a method for synthesizing red phosphorus under vacuum by a CVD method.
  • Patent Document 1 discloses a mechanochemical method using red phosphorus as a raw material.
  • Non-Patent Document 5 discloses a solvothermal reaction method using white phosphorus as a raw material.
  • Patent Document 2 discloses a solvothermal reaction method using red phosphorus as a raw material.
  • Non-Patent Documents 1 to 4 and Patent Document 1 are not suitable for mass synthesis because they require high-temperature and high-pressure treatment or reaction in vacuum.
  • the method disclosed in Non-Patent Document 5 has a problem in safety because toxic white phosphorus is used as a raw material.
  • the black phosphorus obtained by the method described in Patent Document 2 is not sufficient in photocatalytic activity, and there is room for improvement.
  • the present invention has been made in view of the above-mentioned current situation, and is superior in safety to conventional methods, can be synthesized in large quantities, and the obtained black phosphorus-containing composition contains black phosphorus having excellent photocatalytic activity. It is an object of the present invention to provide a method for producing a composition. Another object of the present invention is to provide a novel black phosphorus-containing composition having excellent photocatalytic activity.
  • the present inventors have found that a method in which a raw material composition containing red phosphorus is subjected to a sorbothermal reaction at a temperature higher than 130 ° C. and lower than 180 ° C. is more than a conventional method. It was found that the composition containing black phosphorus obtained is excellent in photocatalytic activity, and is excellent in safety and can be synthesized in large quantities. Furthermore, the present inventors have found that a composition containing black phosphorus in which the aspect ratio of black phosphorus (major axis of average plate surface diameter / average thickness) is in a specific range is excellent in photocatalytic activity, and the above-mentioned problems are brilliantly solved. We came up with the idea that it could be solved and arrived at the present invention.
  • the first invention is a method for producing a composition containing black phosphorus, wherein the production method includes a step of reacting a raw material composition containing red phosphorus with a sorbothermal reaction, and the sorbothermal reaction temperature is set to. It is a method for producing a black phosphorus-containing composition having a temperature higher than 130 ° C. and lower than 180 ° C.
  • the raw material composition containing red phosphorus preferably has a concentration of red phosphorus of 10 g / L or more.
  • the raw material composition containing red phosphorus preferably contains a diamine.
  • the average particle size D50 of the red phosphorus is preferably 10 ⁇ m or more and 2 mm or less.
  • the second invention is a composition containing black phosphorus, which is a black phosphorus-containing composition having an aspect ratio (major axis of average plate surface diameter / average thickness) of 3 to 30.
  • the first method for producing a black phosphorus-containing composition of the present invention has the above-mentioned constitution, is superior in safety to the conventional method, can be synthesized in large quantities, and the obtained composition containing black phosphorus can be obtained. Excellent photocatalytic activity.
  • the second black phosphorus-containing composition of the present invention has the above-mentioned structure and is excellent in photocatalytic activity. Therefore, these black phosphorus-containing compositions can be suitably used as raw materials such as photocatalysts.
  • 6 is an SEM photograph of the black phosphorus-containing composition obtained in Example 5.
  • 6 is an SEM photograph of the black phosphorus-containing composition obtained in Example 8.
  • 6 is an SEM photograph of the black phosphorus-containing composition obtained in Example 9. It is a chart which shows the XRD measurement result of the black phosphorus-containing composition and the commercially available red phosphorus (Comparative Example 3) obtained in Examples 1 and 7. It is a chart which shows the XRD measurement result of the black phosphorus-containing composition and the commercially available red phosphorus (Comparative Example 3) obtained in Examples 5 and 8. 3 is a chart showing Raman spectra of the black phosphorus-containing compositions obtained in Examples 1 to 3 and 7, commercially available red phosphorus (Comparative Example 3), and commercially available black phosphorus (Comparative Example 4).
  • invention simply means the matters common to the first and second inventions.
  • a form in which two or three or more of the individual preferred forms of the present invention described below are combined also falls under the preferred form of the present invention.
  • the first method for producing a black phosphorus-containing composition of the present invention includes a step of solvothermally reacting a raw material composition containing red phosphorus.
  • the reaction temperature in the solvothermal reaction step is higher than 130 ° C and less than 180 ° C.
  • the solvothermal reaction temperature is preferably 130 to 175 ° C, more preferably 140 to 170 ° C, and even more preferably 150 to 160 ° C.
  • the reaction temperature is less than 130 ° C., the yield of black phosphorus is small, and when the reaction temperature is 180 ° C. or higher, the amount of white impurity crystals produced increases and the yield of black phosphorus decreases.
  • the red phosphorus is not particularly limited, but the average particle size D50 is preferably 10 ⁇ m or more and 2 mm or less. As a result, the proportion of black phosphorus in the obtained composition can be further increased, and the photocatalytic activity can be further improved.
  • the D50 of red phosphorus is preferably 1 mm or less. As a result, the reaction of red phosphorus with black phosphorus inside the particles can proceed more sufficiently.
  • the average particle size D50 of red phosphorus is more preferably 10 to 800 ⁇ m, further preferably 20 to 700 ⁇ m, and particularly preferably 30 to 600 ⁇ m.
  • the concentration of red phosphorus in the raw material composition containing red phosphorus is preferably 10 g / L or more.
  • concentration of red phosphorus is stably dissolved in the solvent during the solvothermal reaction, and the formation of crystal phases other than black phosphorus is sufficiently suppressed, so that black phosphorus The yield can be further improved.
  • the proportion of black phosphorus in the obtained composition can be further increased, and the photocatalytic activity can be further improved.
  • the upper limit of the concentration of red phosphorus is not particularly limited, but is preferably 60 g / L or less.
  • the concentration of red phosphorus is more preferably 10 to 60 g / L, further preferably 15 to 45 g / L, and particularly preferably 30 to 45 g / L.
  • the solvent used in the solvothermal reaction is not particularly limited, but it is preferable to use a diamine. That is, the raw material composition containing red phosphorus preferably contains a diamine. As a result, the proportion of black phosphorus in the obtained composition can be further increased, and the photocatalytic activity can be further improved.
  • the diamine is not particularly limited, but for example, the following formula (1);
  • R 1 to R 4 represent the same or different hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 5 represents an alkylene group having 1 to 6 carbon atoms). Examples of the compound to be used.
  • R 1 to R 4 are alkyl groups, the number of carbon atoms is preferably 1 to 3, more preferably 1 to 2, and most preferably 1.
  • the melting point of the compound represented by the formula (1) is in a suitable range, and it can be suitably used for the reaction at less than 180 ° C.
  • the above R 1 to R 4 are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
  • Alkylene group may have a branched chain may be linear in the R 5.
  • the number of carbon atoms in the alkylene groups represented by R 5 is preferably 1-6, more preferably 2-5, more preferably 2-4, particularly preferably 2-3, and most preferably is 2 ..
  • red phosphorus is dissolved stably in the solvent, it is possible to improve the yield of black phosphorus.
  • the diamines are ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,4-butanediamine, 1,5-diaminopentane, and 1,6-diamino.
  • examples thereof include hexane, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine and the like.
  • ethylenediamine and 1,2-propanediamine are preferable.
  • black phosphorus can be obtained in a higher yield.
  • the raw material composition containing red phosphorus may contain other components other than red phosphorus and a solvent.
  • other components include metal nitrate, metal acetate, metal chloride salt, metal acetylsettaneate salt, metal isopropoxide and the like.
  • the content of other components is preferably 0 to 20% by mass with respect to 100% by mass of the raw material composition. It is more preferably 0 to 10% by mass, further preferably 0 to 5% by mass, and most preferably 0 to 3% by mass.
  • the pressure in the solvothermal reaction is not particularly limited, and the reaction can be carried out by the vapor pressure of the solvent at the reaction temperature, but specifically, it is preferably 0.1 to 15 MPa. It is more preferably 0.1 to 10 MPa, still more preferably 0.1 to 5 MPa.
  • the reaction time in the solvothermal reaction is not particularly limited, but is preferably 1 to 168 hours. During this time, the production of black phosphorus proceeds sufficiently and the productivity is also excellent. It is more preferably 6 to 48 hours, still more preferably 12 to 24 hours.
  • the ratio of black phosphorus obtained by combining the reaction temperature in the solvothermal reaction step, the average particle size D50 of red phosphorus, the concentration of red phosphorus, and the preferable form of the solvent. Can be increased sufficiently, and single-phase black phosphorus can also be obtained.
  • Such a method for producing a black phosphorus-containing composition is one of the preferred embodiments of the present invention.
  • the method for producing a black phosphorus-containing composition of the present invention may include a washing step, a drying step, and a pulverization step of the product obtained in the sorbothermal reaction step after the sorbothermal reaction step.
  • the washing step is not particularly limited as long as the product obtained in the sorbothermal reaction step can be washed, but the product is filtered and dispersed in a solvent, and then reduced pressure, normal pressure or pressure filtration is performed. It is preferably carried out by separating the product from the dispersion by centrifugation or decantation. The number of times the washing step is performed is not particularly limited, and is usually 1 to 10 times.
  • As the solvent used for cleaning alcohol such as water or ethanol is preferable. It can be safely washed by using water or ethanol, and the residual solvent can be suppressed in the product.
  • a mode in which the washing step is performed twice in the order of ethanol and water is one of the preferred embodiments of the present invention.
  • the drying step is not particularly limited as long as the solvent can be evaporated from the product obtained in the sorbothermal reaction step or the washing step and dried, but for example, it is dried using a vacuum dryer, a freeze dryer, or the like. Is preferable.
  • the drying temperature is not particularly limited and can be carried out at ⁇ 60 ° C. to 150 ° C.
  • the drying step may be carried out under normal pressure or reduced pressure, but the form of vacuum drying is one of the preferred embodiments of the present invention. By vacuum drying, volatile components can be efficiently removed.
  • the drying time is not particularly limited, and is usually 1 to 24 hours, preferably 5 to 15 hours. If the drying time is 1 hour or more, the residual volatile components can be more sufficiently suppressed, and if the drying time is 24 hours or less, the decrease in productivity can be more sufficiently suppressed.
  • the pulverization step is not particularly limited as long as the product obtained in the sorbothermal reaction step can be pulverized, but can be pulverized using, for example, a mortar, a ball mill, a planetary ball mill, or the like. Further, the obtained product may be pulverized by irradiating with ultrasonic waves. By irradiating ultrasonic waves to pulverize, impurities mixed from the pulverized media can be suppressed to a low level.
  • the average particle size D50 of black phosphorus obtained by the first production method of the present invention is preferably 0.1 to 1000 ⁇ m. It is more preferably 0.5 to 500 ⁇ m, further preferably 1 to 200 ⁇ m, and particularly preferably 1 to 100 ⁇ m.
  • the thickness of 0.1 to 1000 ⁇ m is preferable because the dispersion in the dispersion medium is improved when the black phosphorus particles are processed into a paint or the like.
  • the average particle size D50 can be measured by the method described in Examples.
  • the specific surface area of black phosphorus obtained by the first production method of the present invention is preferably 0.1 to 100 m 2 / g. It is more preferably 0.1 to 30 m 2 / g, further preferably 0.1 to 10 m 2 / g, and particularly preferably 0.1 to 5 m 2 / g. Black phosphorus having a specific surface area of 0.1 to 100 m 2 / g has good dispersibility when processed into a paint or the like, and can be adjusted to an optimum viscosity. The specific surface area can be measured by the method described in Examples.
  • the second invention is also a composition containing black phosphorus, which is a black phosphorus-containing composition having an aspect ratio (major axis of average plate surface diameter / average thickness) of 3 to 30.
  • Black phosphorus having an aspect ratio of 3 to 30 has a plate-like shape and is superior in photocatalytic activity to amorphous black phosphorus.
  • the aspect ratio is preferably 3 to 30, more preferably 5 to 30, and even more preferably 10 to 30. When the aspect ratio is 3 to 30, it is possible to more sufficiently suppress the shape of the particles from being broken and the crystallinity from being lowered, and the particles can be suitably processed into paints and the like.
  • the aspect ratio is measured by the method described in Examples.
  • the black phosphorus-containing composition may contain red phosphorus as an impurity.
  • the average particle size D50 of the second black phosphorus of the present invention is preferably 0.1 to 1000 ⁇ m. It is more preferably 0.5 to 500 ⁇ m, further preferably 1 to 200 ⁇ m, and particularly preferably 1 to 100 ⁇ m.
  • the average particle size D50 can be measured by the method described in Examples. If the average particle size D50 of black phosphorus is 0.1 to 1000 ⁇ m, the dispersibility during processing into a paint or the like is further improved.
  • the specific surface area of the second black phosphorus of the present invention is preferably 0.1 to 100 m 2 / g. It is more preferably 0.1 to 30 m 2 / g, further preferably 0.1 to 10 m 2 / g, and particularly preferably 0.1 to 5 m 2 / g. Black phosphorus having a specific surface area of 0.1 to 100 m 2 / g can be adjusted to an optimum viscosity when processed into a paint or the like. The specific surface area can be measured by the method described in Examples.
  • the method for producing the black phosphorus-containing composition of the second invention is not particularly limited, but it is preferably produced by the method for producing the black phosphorus-containing composition of the first invention. More preferably, in the solvothermal reaction step, the reaction temperature is higher than 130 ° C. and lower than 180 ° C., the raw material composition contains diamine, and the concentration of red phosphorus is 10 g / L or more. .. Such a second method for producing a composition containing black phosphorus of the present invention is also one of the present inventions. From the viewpoint of setting the aspect ratio of black phosphorus in a more preferable range, 1,2-propanediamine is preferable as the diamine.
  • the use of the black phosphorus-containing composition obtained by the first production method of the present invention and the second black phosphorus-containing composition of the present invention is not particularly limited, and the battery material, photocatalytic material, thermoelectric conversion material, and light detection sensor are not particularly limited. , Can be suitably used for field effect transistors and the like. Above all, it is preferably used for photocatalytic applications.
  • the photocatalytic material containing the black phosphorus-containing composition is also one of the present inventions.
  • the photocatalyst material is not particularly limited as long as it contains a black phosphorus-containing composition, but the content thereof is preferably 5 to 100% by mass with respect to 100% by mass of the photocatalyst material. More preferably, it is 30 to 100% by mass.
  • the photocatalytic material may contain other components other than the black phosphorus-containing composition.
  • other components include cocatalysts, mediators, photocatalysts other than black phosphorus, and the like.
  • co-catalyst examples include platinum, gold, silver, ruthenium, ruthenium oxide, cobalt oxide, nickel phosphate, cobalt phosphate and the like. Of these, platinum is preferable.
  • the mediator is preferably a conductive substance, and examples thereof include gold fine particles and graphene.
  • the position of the valence band is preferably located at a position nobler than the redox potential of water / oxygen, and when used in combination with the black phosphorus-containing composition, photocatalytic total decomposition of water can be achieved. It will be possible.
  • the photocatalyst other than black phosphorus include titanium oxide, tungsten oxide, bismuth vanadate, tantalum nitride and the like.
  • the total content of the other components in the photocatalyst material is preferably 0.1 to 60% by mass with respect to 100% by mass of the photocatalyst material. More preferably, it is 0.1 to 50% by mass.
  • the content of the co-catalyst in the photocatalyst material is preferably 0.1 to 5% by mass with respect to 100% by mass of the photocatalyst material. More preferably, it is 0.2 to 3% by mass.
  • the content of the mediator in the photocatalyst material is preferably 0.1 to 20% by mass with respect to 100% by mass of the photocatalyst material. More preferably, it is 0.2 to 10% by mass.
  • the content of the photocatalyst other than black phosphorus in the photocatalyst material is preferably 0.1 to 60% by mass with respect to 100% by mass of the photocatalyst material. More preferably, it is 0.1 to 50% by mass.
  • Example 1 0.3 g of red phosphorus (PPE02PB, manufactured by High Purity Chemical Laboratory Co., Ltd.) and 20 mL of ethylenediamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are enclosed in an autoclave and placed in a static autoclave container lined with Teflon (registered trademark). The slurry was transferred and heated at 160 ° C. for 24 hours. After heating, the slurry was filtered, washed in the order of ethanol and ion-exchanged water, and vacuum dried at 50 ° C. for 12 hours to obtain a black powder.
  • PPE02PB red phosphorus
  • ethylenediamine manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Example 2 Production was carried out in the same manner as in Example 1 except that the mass of red phosphorus was changed to 0.6 g, and a black powder was obtained.
  • Example 3 Production was carried out in the same manner as in Example 1 except that the mass of red phosphorus was changed to 0.9 g, and a black powder was obtained.
  • Example 4 Production was carried out in the same manner as in Example 2 except that the heating temperature was changed to 140 ° C. to obtain a black powder.
  • Example 5 The production was carried out in the same manner as in Example 1 except that the red phosphorus was changed to one that passed through a mesh of 30 ⁇ m, and a brown powder was obtained.
  • Example 6 Production was carried out in the same manner as in Example 1 except that the particle size of red phosphorus was changed to 1.3 mm to obtain reddish brown lumpy particles.
  • Example 7 Production was carried out in the same manner as in Example 1 except that the mass of red phosphorus was changed to 0.2 g to obtain a brown powder.
  • Example 8 Production was carried out in the same manner as in Example 2 except that the solvent was changed to 1,2-propanediamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to obtain a reddish brown powder.
  • the shape of this powder was plate-like, and the aspect ratio was 12.1.
  • Example 9 The production was carried out in the same manner as in Example 8 except that red phosphorus was changed to one that passed through a mesh of 30 ⁇ m, and a reddish brown powder was obtained.
  • the shape of this powder was plate-like, and the aspect ratio was 19.5.
  • ⁇ Average particle size D50 particle size distribution
  • the particle size distribution of each sample was measured with a laser diffraction type particle size distribution measuring device (Microtrac MT3000 manufactured by Nikkiso Co., Ltd.) to obtain a particle size distribution curve.
  • the powder (powder) to be measured was charged so that the transmittance was 0.70 to 0.99, and the measurement was carried out at a flow velocity of 60% while ultrasonically dispersing and circulating. Water was used as the dispersion medium at the time of measurement, and sodium hexametaphosphate was used as the dispersant.
  • the particle size value when the integrated value was 50% in the obtained volume-based particle size distribution curve was defined as the average particle size D50.
  • MiniFlex 600 manufactured by Rigaku Co., Ltd.
  • a measurement sample was prepared by supporting 0.5% by mass of platinum fine particles as a co-catalyst on the compositions obtained in Examples 1 to 9 and Comparative Example 2 or commercially available red phosphorus as Comparative Example 3.
  • a 0.05 g measurement sample and 10 ml of a 20% by volume methanol aqueous solution were placed in a 20 mL quartz cell, and the hydrogen when irradiated with light was subjected to gas chromatography (TCD-GC, GC-8A manufactured by Shimadzu Corporation). analyzed.
  • Gas chromatography TCD-GC, GC-8A manufactured by Shimadzu Corporation.
  • Light reflected from a 300 W xenon lamp with a visible light cold mirror and passed through a sharp cut filter (Sigma Kouki Co., Ltd. SCF-50S-42L) was used as a light source.
  • the rate of hydrogen production per unit time 1 hour and 5 hours after light irradiation was calculated, and the photocatalytic activity (catalytic activity) was evaluated.
  • Table 3 shows the physical characteristics of the production conditions and products of Examples 1 to 9 and Comparative Examples 1 and 2, commercially available red phosphorus as Comparative Example 3, and commercially available black phosphorus as Comparative Example 4.
  • the peaks near 10 ° and 31 ° in Example 1 are diffraction lines due to the secondary structure due to the orientation of the black phosphorus nanoparticles, and are derived from black phosphorus.
  • the peak of 15 to 16 ° in XRD was derived from red phosphorus, and the red phosphorus content of the sample in Example 1 was below the detection limit. From this, only the diffraction line derived from black phosphorus was observed in Example 1.
  • the plate-shaped black phosphorus has a specifically high peak intensity at 2 ⁇ of 15.6 °. This peak is attributed to the (020) plane of black phosphorus. Considering the high peak intensity of the (020) plane in FIG. 5 and the SEM image of FIG. 1, it can be seen that the black phosphorus of Example 8 has a plate-like shape in which the (020) plane is grown.

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Abstract

La présente invention concerne un procédé de production d'une composition contenant du phosphore noir qui présente une sécurité supérieure à celle de procédés classiques, et permet la synthèse de plus grandes quantités de la composition contenant du phosphore noir que les procédés classiques, et dans lequel la composition contenant du phosphore noir obtenue présente une excellente activité photocatalytique. La présente invention concerne un procédé de production d'une composition contenant du phosphore noir, le procédé de production de la composition contenant du phosphore noir étant caractérisé en ce qu'une étape de réaction solvothermique d'une composition de matière première comprenant du phosphore rouge est incluse, et la température de réaction solvothermique est supérieure à 130 °C et inférieure à 180 °C.
PCT/JP2020/023168 2019-06-27 2020-06-12 Procédé de production d'une composition contenant du phosphore noir, et composition contenant du phosphore noir WO2020262035A1 (fr)

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Cited By (1)

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CN113477267A (zh) * 2021-06-09 2021-10-08 东华理工大学 氮氧化磷光催化还原含铀废水的应用

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