WO2017056613A1 - Procédé de production de particules de dioxyde de vanadium - Google Patents

Procédé de production de particules de dioxyde de vanadium Download PDF

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Publication number
WO2017056613A1
WO2017056613A1 PCT/JP2016/069700 JP2016069700W WO2017056613A1 WO 2017056613 A1 WO2017056613 A1 WO 2017056613A1 JP 2016069700 W JP2016069700 W JP 2016069700W WO 2017056613 A1 WO2017056613 A1 WO 2017056613A1
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Prior art keywords
vanadium dioxide
dioxide particles
vanadium
particles
hydrothermal reaction
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PCT/JP2016/069700
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English (en)
Japanese (ja)
Inventor
啓司 新井
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コニカミノルタ株式会社
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Publication of WO2017056613A1 publication Critical patent/WO2017056613A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy

Definitions

  • the present invention relates to a method for producing vanadium dioxide particles. More specifically, the present invention relates to a method for producing vanadium dioxide particles exhibiting excellent thermochromic properties.
  • thermochromic material a material having thermochromic properties
  • thermochromic material is a material whose optical properties such as transparent state / reflective state change depending on temperature. Specifically, the material is in a reflective state when the temperature is high, and is in a transparent state when the temperature is low. When such a thermochromic material is applied to a window glass of a building, for example, it can reflect sunlight in the summer to block heat, and in winter it can transmit sunlight and use heat, As a result, both energy saving and comfort can be achieved.
  • thermochromic materials that has received most attention is vanadium dioxide particles containing vanadium dioxide (VO 2 ) (hereinafter also simply referred to as “VO 2 particles”).
  • VO 2 particles are known to exhibit thermochromic properties (property of reversibly changing optical characteristics depending on temperature) during phase transition near room temperature. Therefore, thermochromic properties depending on the temperature of the environment can be obtained by utilizing this property.
  • vanadium oxide has a plurality of polymorphs of oxides and crystal phases of trivalent to pentavalent vanadium.
  • crystal phases such as A phase, B phase, C phase and R phase (so-called “rutile crystal phase”).
  • R phase the main crystal structure exhibiting thermochromic properties as described above. Since this R phase has a monoclinic structure below the transition temperature, it is also called an M phase.
  • M phase the monoclinic structure below the transition temperature
  • the particles are not aggregated, the particle size is nano-order (100 nm or less), and the particles are isotropic. It is desirable to have
  • thermochromic member such as a film
  • a VO 2 particle or a dispersion thereof is prepared and bonded to a member that is desired to exhibit thermochromic properties via an adhesive. It has been studied to manufacture a member having chromic properties (see, for example, Patent Document 1 and Patent Document 2).
  • the VO 2 particles described in Patent Document 1 are produced by a hydrothermal reaction.
  • the particles grow anisotropically into a rod shape, the particle size is large and good thermochromic properties are obtained. There is a problem that can not be.
  • hydrazine is used as a reducing agent to reduce the particle size.
  • the particles are aggregated during the growth process, it is difficult to control the particle size and thermochromic property. is there.
  • the present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is to provide a method for producing vanadium dioxide particles exhibiting excellent thermochromic properties.
  • the present inventor formed vanadium dioxide particles by hydrothermal reaction in the process of studying the cause of the above problems, etc., and oxidized the vanadium dioxide particles, thereby providing excellent thermochromic properties.
  • the inventors have found that vanadium dioxide particles exhibiting the following can be produced, and have reached the present invention. That is, the said subject which concerns on this invention is solved by the following means.
  • a method for producing vanadium dioxide particles containing vanadium dioxide having thermochromic properties A step of forming the vanadium dioxide particles by hydrothermal reaction of a reaction solution containing a raw material containing a vanadium compound, a reducing agent and water; Oxidizing the vanadium dioxide particles;
  • a method for producing vanadium dioxide particles comprising:
  • Item 4 The method for producing vanadium dioxide particles according to any one of Items 1 to 3, wherein a temperature of the hydrothermal reaction is in a range of 250 to 350 ° C.
  • the vanadium dioxide particles are tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), tin (Sn), rhenium (Re), iridium (Ir), osmium (Os), antimony (Sb).
  • the method for producing vanadium dioxide particles according to any one of items 1 to 5, wherein:
  • the above-mentioned means of the present invention can provide a method for producing vanadium dioxide particles exhibiting excellent thermochromic properties.
  • thermochromic property is improved.
  • the method for producing vanadium dioxide particles according to the present invention is a method for producing vanadium dioxide particles containing vanadium dioxide having thermochromic properties, and a hydrothermal reaction of a reaction solution containing a raw material containing a vanadium compound, a reducing agent and water. And the step of forming the vanadium dioxide particles and the step of oxidizing the vanadium dioxide particles.
  • This feature is a technical feature common to or corresponding to the claimed invention.
  • the pH at 25 ° C. of the reaction solution after the hydrothermal reaction is within the range of 4.0 to 7.0. This is preferable because the stability of the vanadium dioxide particles is improved.
  • the oxidation-reduction potential at 25 ° C. of the reaction solution after the hydrothermal reaction is in the range of 100 to 500 mV because the surface oxidation of the particles can be appropriately advanced.
  • the temperature of the hydrothermal reaction when the temperature of the hydrothermal reaction is in the range of 250 to 350 ° C., metastable rod-like vanadium dioxide particles that are impurities are less likely to be produced, and vanadium dioxide exhibiting an M phase. It is preferable because the particles are small and have a uniform size.
  • reaction time of the hydrothermal reaction is preferably within the range of 12 to 72 hours.
  • the vanadium dioxide particles are tungsten (W), molybdenum (Mo), niobium (Nb), tantalum (Ta), tin (Sn), rhenium (Re), iridium (Ir), osmium (Os). ), Antimony (Sb), ruthenium (Ru), germanium (Ge), chromium (Cr), iron (Fe), gallium (Ga), aluminum (Al), fluorine (F) and phosphorus (P). It is preferable in that the phase transition temperature can be changed by containing the selected element.
  • pH in 25 degreeC conversion means the value of pH at the time of measuring pH of a measuring object (in this invention, it is a reaction liquid mainly) at 25 degreeC.
  • the method for producing vanadium dioxide particles according to the present invention is a method for producing vanadium dioxide particles containing vanadium dioxide having thermochromic properties, and a hydrothermal reaction of a reaction solution containing a raw material containing a vanadium compound, a reducing agent and water. And the step of forming the vanadium dioxide particles and the step of oxidizing the vanadium dioxide particles.
  • vanadium dioxide particles containing vanadium dioxide having thermochromic properties of the present invention VO 2 (hereinafter, also referred to as "VO 2 particles”.
  • a reaction solution is prepared by mixing a solution containing a reducing agent, water, and a compound containing vanadium (V) (hereinafter also referred to as “vanadium compound”).
  • This reaction solution may be an aqueous solution in which the vanadium compound is dissolved in water, or may be a suspension in which the vanadium compound is dispersed in water.
  • the pH of the reaction solution after hydrothermal reaction is preferably in the range of 4.0 to 7.0 because the stability of the vanadium dioxide particles in the reaction solution is improved.
  • the compound containing vanadium (V) is not particularly limited as long as it is a compound containing at least pentavalent vanadium (V).
  • vanadium pentoxide V 2 O 5
  • ammonium vanadate NH 4
  • VO 3 vanadium trichloride oxide
  • NaVO 3 sodium metavanadate
  • the reaction liquid according to the present invention may contain a metal compound other than vanadium (V).
  • the metal compound contained other than vanadium (V) is not particularly limited as long as it does not inhibit the effects of the present invention.
  • the metal compound other than vanadium (V) tungsten (W ), Molybdenum (Mo), niobium (Nb), tantalum (Ta), tin (Sn), rhenium (Re), iridium (Ir), osmium (Os), antimony (Sb), ruthenium (Ru), germanium (Ge) ), Chromium (Cr), iron (Fe), gallium (Ga), aluminum (Al), fluorine (F), and phosphorus (P).
  • the metal compound other than vanadium (V) may be a vanadium compound having a valence different from that of vanadium (V), for example, V 2 O 3 (a trivalent vanadium compound).
  • V 2 O 4 tetravalent vanadium compound
  • V 6 O 13 4.3 valent vanadium compound
  • a metal compound other than vanadium (V) can be contained in the reaction solution to change the phase transition temperature exhibiting thermochromic properties, it is also preferable to add it as an additive.
  • the reducing agent used in the present invention may be easily dissolved in water and may function as a reducing agent for compounds containing vanadium (V).
  • a reducing agent for compounds containing vanadium (V) for example, hydrazine (N 2 H 4 ) and hydrazine Hydrazine hydrate (N 2 H 4 .nH 2 O) such as monohydrate and the like can be mentioned.
  • the reducing agent has a thermochromic property (in terms of a molar ratio of 1.0 to 1.4 equivalents with respect to the compound containing vanadium (V)). Vanadium dioxide particles containing VO 2 exhibiting an M phase crystal phase) are preferred because they can be selectively obtained.
  • reaction liquid according to the present invention may be a mixture of substances having oxidizing properties or reducing properties.
  • materials include, for example, hydrogen peroxide (H 2 O 2 ).
  • H 2 O 2 hydrogen peroxide
  • the pH of the reaction solution can be adjusted, or the vanadium compound can be uniformly dissolved.
  • hydrogen peroxide hydrogen peroxide water (concentration 35 mass%, the Wako Pure Chemical Industries make, special grade) can be used suitably, for example.
  • hydrothermal reaction treatment is performed using the prepared reaction solution to form vanadium dioxide particles. That is, in this step, the reaction liquid containing a metal compound other than vanadium (V) is subjected to a hydrothermal reaction.
  • hydrothermal reaction means a chemical reaction that occurs in hot water (subcritical water) whose temperature and pressure are lower than the critical point of water (374 ° C., 22 MPa).
  • a hydrothermal reaction process is implemented in an autoclave apparatus, for example. By the hydrothermal reaction treatment, VO 2 particles containing vanadium dioxide (VO 2 ) are obtained.
  • the conditions of the hydrothermal reaction treatment are appropriately set.
  • the liquid temperature of the hydrothermal reaction treatment is, for example, 250 to 350 ° C. (preferably 270 to 350 ° C., more preferably 300 to 350 ° C.).
  • the hydrothermal reaction is carried out within a liquid temperature range of 250 to 350 ° C., metastable rod-like vanadium dioxide particles that are impurities are less likely to be produced, and the vanadium dioxide particles exhibiting the M phase have a small and uniform particle size. This is preferable.
  • the hydrothermal reaction treatment time is, for example, 1 hour to 7 days, and by increasing the time, the average particle diameter of the obtained VO 2 particles can be controlled, and within 7 days, The possibility of excessive energy consumption can be avoided. More preferably, it is in the range of 12 to 72 hours from the viewpoint of cost.
  • the hydrothermal reaction is preferably performed while stirring, because the particle diameter of the VO 2 particles can be made more uniform.
  • the hydrothermal reaction process may be implemented by a batch type and may be implemented by a continuous type.
  • the reaction solution is oxidized. Specifically, the reaction solution obtained in the particle formation step is cooled to room temperature to oxidize the vanadium dioxide particles.
  • the oxidation method include a method in which the reaction solution is allowed to stand at room temperature, a method in which an oxidizing agent is added, and a method in which oxygen bubbling is performed.
  • the pH at 25 ° C. of the reaction solution after the hydrothermal reaction is preferably in the range of 4.0 to 7.0.
  • the redox potential is preferably in the range of 100 to 500 mV. It is preferable that the pH is within the range because the stability of the vanadium dioxide particles in the reaction solution is improved. Furthermore, it is preferable that the oxidation-reduction potential is within the above range in that the surface oxidation of the particles can be appropriately advanced.
  • the room temperature is, for example, room temperature in the production facility, and specifically, for example, around 25 ° C.
  • oxidant used in the present invention halogen, hypohalous acid, halous acid, perhalogen acid or salts thereof, halogen oxide, peroxide and the like, and known oxidants can be used.
  • the reaction solution containing the VO 2 particles containing the vanadium dioxide (VO 2) having a thermochromic property can be obtained. Thereafter, VO 2 particles according to the present invention are obtained from the reaction solution by filtration, washing, drying and the like.
  • Vanadium dioxide particles (VO 2 particles) VO 2 particles produced by the production method of the VO 2 particles of the present invention contains vanadium dioxide (VO 2), and can provide a vanadium dioxide particles having excellent thermochromic.
  • the average particle diameter of the VO 2 particles is preferably in the range of 5 to 50 nm.
  • the CV value of the particle size distribution of the VO 2 particles is preferably 40 or less.
  • thermochromic properties The thermochromic property of the aqueous dispersion containing vanadium dioxide particles can be measured by using, for example, a spectrophotometer V-670 (manufactured by JASCO Corporation), the light transmittance at a wavelength of 1300 nm that is not affected by the absorption peak of water. It can be measured as a difference.
  • the vanadium dioxide particles produced by the method for producing vanadium dioxide particles according to the present invention are subjected to an oxidation step, so that the ratio of oxygen atoms on the particle surface is increased as compared with conventional vanadium particles exhibiting thermochromic properties. It is thought that there is.
  • the composition of the surface of the vanadium dioxide particles can be measured by a known method, for example, by X-ray photoelectron spectroscopy (XPS: X-ray Photoelectron Spectroscopy).
  • XPS measurement is a technique for irradiating a sample with X-rays and measuring photoelectron energy emitted from the sample. Photoelectrons emitted from deep inside the sample are not scattered because they are not scattered within the sample, and the state near the surface can be evaluated. Therefore, the XPS measurement can detect the surface state within several to several tens of nanometers of the sample. Specifically, the XPS measurement can be performed with an X-ray electron spectrometer (Quantum-2000, manufactured by ULVAC-PHI). The measurement conditions may vary depending on the type of phosphor to be measured, the particle shape, and the like. For example, measurement can be performed under the following measurement conditions.
  • VO 2 particles according to the present invention may contain other compounds or atoms within a range not adversely affecting the effects of the present invention in addition to vanadium dioxide as described above.
  • VO 2 particles VO 2 particles produced by the production method of the present invention are dispersed in water, and vanadium dioxide (VO 2), and a dispersion containing VO 2 particles having a thermochromic Can be provided. If the dispersion containing VO 2 particles produced by the method for producing VO 2 particles of the present invention is applied, an optical film showing excellent thermochromic properties can be provided.
  • distributing should just contain water, and well-known solvents, such as an organic solvent, can be used in the range which does not inhibit the function of vanadium dioxide.
  • the solution stirred for 1 hour after dropping is put into a commercially available autoclave for hydrothermal reaction treatment (manufactured by Sanai Kagaku Co., HU-50) (SUS body is equipped with a 50 ml capacity Teflon (registered trademark) inner cylinder). And hydrothermal reaction at 250 ° C. for 48 hours to obtain a reaction solution. A portion of the reaction solution was immediately diluted 5000 times with pure water to evaluate thermochromic properties.
  • the solution stirred for 1 hour after dropping is put into a commercially available autoclave for hydrothermal reaction treatment (manufactured by Sanai Kagaku Co., HU-50) (SUS body is equipped with a 50 ml capacity Teflon (registered trademark) inner cylinder). And hydrothermal reaction at 250 ° C. for 48 hours to obtain a reaction solution.
  • the reaction solution was transferred to a glass bottle and allowed to stand at 25 ° C. for 72 hours in the atmosphere, and then diluted 5000 times with pure water to evaluate thermochromic properties.
  • the solution stirred for 1 hour after dropping is put into a commercially available autoclave for hydrothermal reaction treatment (manufactured by Sanai Kagaku Co., HU-50) (SUS body is equipped with a 50 ml capacity Teflon (registered trademark) inner cylinder).
  • a hydrothermal reaction was performed at 270 ° C. for 48 hours to obtain a reaction solution.
  • the reaction solution was transferred to a glass bottle and oxygen bubbling was performed at 10 ml / min for 3 hours, and then the thermochromic properties of the reaction solution were evaluated.
  • ⁇ Thermochromic properties (change in light transmittance)>
  • a hydrothermally diluted reaction solution diluted 5000 times with pure water is placed in a commercially available quartz cell with a stopper (two-sided translucent 45 ⁇ 12.5 ⁇ 10 mm), and a spectrophotometer that can be heated (V-manufactured by JASCO Corporation). 670 type, 190-2500 nm) was used, and the measurement temperatures were 20 ° C. and 80 ° C.
  • the temperature dependence of the light transmittance (%; wavelength 1300 nm) of the reaction solution was measured.
  • vanadium dioxide particles exhibiting excellent thermochromic properties can be produced, and these can be suitably used for near infrared light shielding films and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un procédé de production de particules de dioxyde de vanadium qui présentent un excellent caractère thermochromique. L'invention concerne un procédé de production de particules de dioxyde de vanadium contenant du dioxyde de vanadium thermochromique, ledit procédé comprenant une étape consistant à former des particules de dioxyde de vanadium en soumettant une solution de réaction comprenant de la matière première contenant un composé de vanadium, un agent réducteur, et de l'eau à une réaction hydrothermique et une étape consistant à oxyder les particules de dioxyde de vanadium.
PCT/JP2016/069700 2015-09-30 2016-07-01 Procédé de production de particules de dioxyde de vanadium WO2017056613A1 (fr)

Applications Claiming Priority (2)

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JP2015-192610 2015-09-30
JP2015192610A JP2018188489A (ja) 2015-09-30 2015-09-30 二酸化バナジウム粒子の製造方法

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WO2017056613A1 true WO2017056613A1 (fr) 2017-04-06

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011178825A (ja) * 2010-02-26 2011-09-15 National Institute Of Advanced Industrial Science & Technology 単結晶微粒子、その製造方法、及びその用途
JP2014505651A (ja) * 2011-01-21 2014-03-06 中国科学院上海硅酸塩研究所 ドーピング二酸化バナジウム粉体、分散液及びそれらの製造方法と応用
WO2016052740A1 (fr) * 2014-10-03 2016-04-07 コニカミノルタ株式会社 Film optique et processus de production de film optique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011178825A (ja) * 2010-02-26 2011-09-15 National Institute Of Advanced Industrial Science & Technology 単結晶微粒子、その製造方法、及びその用途
JP2014505651A (ja) * 2011-01-21 2014-03-06 中国科学院上海硅酸塩研究所 ドーピング二酸化バナジウム粉体、分散液及びそれらの製造方法と応用
WO2016052740A1 (fr) * 2014-10-03 2016-04-07 コニカミノルタ株式会社 Film optique et processus de production de film optique

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