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WO2015190888A1 - Procédé de fabrication de nanoparticules métalliques creuses, et nanoparticules métalliques creuses fabriquées ainsi - Google Patents

Procédé de fabrication de nanoparticules métalliques creuses, et nanoparticules métalliques creuses fabriquées ainsi Download PDF

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Publication number
WO2015190888A1
WO2015190888A1 PCT/KR2015/005969 KR2015005969W WO2015190888A1 WO 2015190888 A1 WO2015190888 A1 WO 2015190888A1 KR 2015005969 W KR2015005969 W KR 2015005969W WO 2015190888 A1 WO2015190888 A1 WO 2015190888A1
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Prior art keywords
hollow metal
metal nanoparticles
hollow
nanoparticles
manufacturing
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English (en)
Korean (ko)
Inventor
김광현
김상훈
황교현
조준연
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LG Chem Ltd
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LG Chem Ltd
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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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds

Definitions

  • the present application relates to a method for producing hollow metal nanoparticles and hollow metal nanoparticles produced thereby.
  • Nanoparticles are nanoscale particle sizes, which are completely different from bulk materials due to their large specific surface area and quantum confinement effect, in which the energy required for electron transfer varies with the size of the material. , Electrical and magnetic properties. Therefore, because of these properties, much attention has been focused on its application in the field of catalysts, electromagnetism, optics, medicine and the like. Nanoparticles are intermediates between bulk and molecules, and are capable of synthesizing nanoparticles in terms of a two-way approach, a "top-down” approach and a “bottom-up” approach.
  • Synthesis methods of metal nanoparticles include a method of reducing metal ions with a reducing agent in a solution, a method using gamma rays, and an electrochemical method, but conventional methods are difficult to synthesize nanoparticles having a uniform size and shape, or organic solvents.
  • the economical mass production of high quality nanoparticles has been difficult due to various reasons, such as environmental pollution and high cost.
  • hollow metal nanoparticles particles having a lower reduction potential such as Ag, Cu, Co, and Ni are synthesized, and then potential substitution is performed with metals having a higher reduction potential than these, for example, Pt, Pd, or Au.
  • Hollow metal nanoparticles were prepared by dissolving Ag, Cu, Co, Ni, and the like on the surface of particles, and dissolving Ag, Cu, Co, Ni, etc. remaining inside through acid treatment after surface replacement. In this case, there is a problem in the process that needs to be post-treated with an acid, and since the potentiometric substitution method is a natural reaction, it is difficult to prepare uniform particles because there are few factors that can be controlled.
  • the problem to be solved by the present application is to provide a method for producing hollow metal nanoparticles that can be easily mass-produced at low cost without environmental pollution to solve the above problems.
  • Another problem to be solved by the present application is to provide a hollow metal nanoparticles produced by the above production method.
  • One embodiment of the present application comprises the steps of preparing a solution comprising a first metal salt, a second metal salt, a stabilizer and a solvent; And mixing the solution and the reducing agent to form hollow metal nanoparticles.
  • Another embodiment of the present application provides a hollow metal nanoparticles prepared by the above production method.
  • the manufacturing method it is possible to mass-produce hollow metal nanoparticles having a uniform size to several nanometers, reduce costs, and use a surfactant, so that the process is simple. Because there is no organic solvent in the manufacturing process, there is an advantage that there is no environmental pollution.
  • Figure 1 shows a transmission electron microscope (TEM) image of the hollow metal nanoparticles prepared according to Experimental Example 1.
  • Figure 2 shows a transmission electron microscope (TEM) image of the hollow metal nanoparticles prepared according to Experimental Example 2.
  • Figure 3 shows a transmission electron microscope (TEM) image of the nanoparticles prepared according to Experimental Example 3.
  • Figure 4 shows a transmission electron microscope (TEM) image of the hollow metal nanoparticles prepared according to Experimental Example 4.
  • Figure 5 shows a transmission electron microscope (TEM) image of the hollow metal nanoparticles prepared according to Experimental Example 5.
  • Figure 6 shows a transmission electron microscope (TEM) image of the nanoparticles prepared according to Experimental Example 6.
  • Figure 7 shows a transmission electron microscope (TEM) image of the nanoparticles prepared according to Experimental Example 7.
  • Figure 8 shows a transmission electron microscope (TEM) image of the nanoparticles prepared according to Experimental Example 7.
  • hollow means that the core portion of the hollow metal nanoparticle is empty.
  • the hollow may be used as the same meaning as the hollow core.
  • the hollow includes the terms hollow, hole, void, porous.
  • the hollow may comprise a space in which no internal material is present at least 50% by volume, specifically at least 70% by volume, more specifically at least 80% by volume.
  • at least 50% by volume, specifically 70% by volume, more specifically 80% by volume may include an empty space.
  • a manufacturing method includes preparing a solution including a first metal salt, a second metal salt, a stabilizer, and a solvent; And mixing the solution and the reducing agent to form hollow metal nanoparticles.
  • the mixing of the solution and the reducing agent may be adding a reducing agent to the solution.
  • the preparation method may use a surfactant at 0.1 mol% or less relative to the first metal salt.
  • the surfactant in the preparation method may be 0 mol% relative to the first metal salt.
  • the manufacturing method may not use a surfactant. Since the manufacturing method does not use a surfactant, it is advantageous in mass production because it is cost-effective and has an advantage in that it is an environmentally friendly process.
  • the surfactant may be adjacent to the metal ions to surround the particle surface or remain in the hollow interior, thereby making it difficult to access the reactants when used in the catalytic reaction. Thus, there is a need for a post-process to remove the surfactant. Therefore, when not using the surfactant according to one embodiment of the present application, there is an advantage that the manufacturing method is simple, there is a cost-saving effect is also advantageous in mass production.
  • the first metal salt or the second metal salt may be ionized in a solution to provide atomic group ions including metal ions or metal ions.
  • the first metal salt may comprise a first metal and the second metal salt may comprise a second metal.
  • the first metal may be different from the second metal.
  • the first metal or the second metal is different from each other, and may be selected from the group consisting of metals, metalloids, lanthanum group metals, and actinium group metals belonging to groups 3 to 15 of the periodic table.
  • the first metal is specifically platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), Cr (chromium), titanium (Ti), gold (Au), cerium (Ce), silver (Ag) and copper (Cu) may be at least one selected from the group consisting of.
  • ruthenium ruthenium
  • Rh rhodium
  • Mo molybdenum
  • Ir iridium
  • rhenium palladium
  • V vanadium
  • W tungsten
  • Co cobalt
  • iron iron
  • Se selenium
  • Ni nickel
  • Bi bismuth
  • Sn tin
  • Cr chromium
  • Ti titanium
  • Ce cerium
  • Cu copper
  • It may be selected from the group, it may be even more specifically nickel (Ni).
  • the second metal is different from the first metal, and specifically, platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), or iridium (Ir) , Rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn) It may be one selected from the group consisting of Cr (chromium), titanium (Ti), gold (Au), cerium (Ce), silver (Ag) and copper (Cu). More specifically, it may be selected from the group consisting of platinum (Pt), palladium (Pd), silver (Ag) and gold (Au), even more specifically may be platinum (Pt).
  • the first metal salt may be represented by the following Chemical Formula 1
  • the second metal salt may be represented by the following Chemical Formula 2.
  • X and Y may each independently be an ion of a metal selected from the group consisting of metals, metalloids, lanthanum group metals, and actinium group metals belonging to groups 3 to 15 of the periodic table. .
  • X is specifically platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti), gold (Au), cerium (Ce), silver (Ag) and copper (Cu) may be an ion of a metal selected from the group, more specifically ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel
  • Y is different from X, and platinum (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), and palladium (Pd) ), Vanadium (V), tungsten (W), cobalt (Co), iron (Fe), selenium (Se), nickel (Ni), bismuth (Bi), tin (Sn), chromium (Cr), titanium (Ti) ), Gold (Au), cerium (Ce), silver (Ag) and copper (Cu) may be an ion of a metal selected from the group, more specifically platinum (Pt), gold (Au), silver (Ag ) And palladium (Pd) may be ions of the metal selected from the group consisting of, and more specifically, platinum (Pt) ions.
  • a and C may each independently be a ligand that is a monovalent anion, and specifically, each independently NO 3 ⁇ , NO 2 ⁇ , OH ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , and I - it may be selected from the group consisting of.
  • B may be an ion of an element belonging to Group 1 on the periodic table, and may be selected from the group consisting of H + , K + , Na +, and NH 3 + .
  • m may be 2 or 3
  • p may be 0, 2 or 4
  • q may be 2, 4 or 6.
  • the first metal salt may be specifically NiCl 2 , CoCl 2 , Ni (NO 3 ) 2 , Pd (NO 3 ) 2 or RuCl 3
  • the second metal salt may be specifically K 2 PtCl 4 or K 2 PtCl 6 . .
  • the first metal can provide the cation of Ni 2 +
  • the second metal salt is selected from PtCl 4 2 - anion of the - to be able to provide the anion, the Ni 2 + cations and PtCl 4 2 of Together, the shell portion of the hollow metal nanoparticles can be formed.
  • the molar ratio of the first metal salt and the second metal salt may be 1: 5 to 10: 1, specifically 2: 1 to 5: 1. In the above range, it is preferable to form a shell of the hollow metal nanoparticles.
  • the solvent dissolves the first metal salt and the second metal salt, and may specifically include water.
  • the solvent may be water.
  • the present invention since the present invention does not use an organic solvent as a solvent, there is no need for a post-treatment step of treating the organic solvent in the manufacturing process, and thus there is a cost saving effect and an environmental pollution prevention effect.
  • Forming the solution in one embodiment of the present application may be carried out at a temperature in the range of more than 4 °C 100 °C. Specifically, the temperature may be performed at a temperature of 4 ° C. or higher and 80 ° C. or lower. If the solvent is an organic solvent, there is a problem to be prepared at a high temperature of more than 100 °C and the process costs a lot. When the manufacturing method according to one embodiment of the present application can be manufactured at a low temperature of less than 100 °C because the manufacturing method is simple, there is an advantage in the process, the cost reduction effect is large.
  • Forming the solution in one embodiment of the present application may be performed for 5 minutes to 120 minutes, more specifically 10 minutes to 90 minutes, even more specifically 20 minutes to 60 minutes.
  • the mixing speed of the solution and the reducing agent may be greater than 0.1 ml / h.
  • the mixing may be a rate at which a reducing agent is added to the solution.
  • FIGS. 1 to 3 show transmission electron microscope (TEM) images of hollow metal nanoparticles prepared according to Experimental Examples 1 to 3.
  • FIG. The nanoparticles of FIG. 3 according to Experimental Example 3 with the addition rate of the reducing agent at 0.1 ml / h may be confirmed to be difficult to form hollows.
  • the nanoparticles of FIGS. 1 and 2 according to Experimental Examples 1 and 2 having the addition rate of the reducing agent at 400 ml / h and 100 ml / h, respectively, can be confirmed that the hollows are uniformly formed.
  • the reducing agent is a strong reducing agent of standard reduction -0.23V or less, specifically -4V or more and -0.23V or less, and has a reducing power capable of reducing dissolved metal ions to precipitate as metal particles. It is not specifically limited.
  • Such reducing agent may be, for example, one or two or more selected from the group consisting of NaBH 4 , NH 2 NH 2 , LiAlH 4 and LiBEt 3 H.
  • the stabilizer may include one or two or more selected from the group consisting of disodium phosphate, dipotassium phosphate, disodium citrate, and trisodium citrate.
  • the content of the stabilizer may be 3 to 30 times less than the first metal salt or the second metal salt in molar units, specifically 5 to 25 times, more specifically 10 to 25 times. When the content of the stabilizer is within the above range, hollow metal nanoparticles can be formed uniformly.
  • the stabilizer When the stabilizer is not used, it is difficult to form the hollow metal nanoparticles, and since the first metal salt and the second metal salt may agglomerate with each other to form amorphous particles, it is preferable to use the stabilizer within the above range.
  • the particle diameter of each hollow metal nanoparticle when the average particle diameter of the hollow metal nanoparticles is 100%, the particle diameter of each hollow metal nanoparticle may be included in a range of 80% to 120%. That is, the particle diameter of the hollow metal nanoparticles may be 80% to 120% of the average particle diameter of the hollow metal nanoparticles. If it is out of the above range, since the size of the hollow metal nanoparticles becomes entirely non-uniform, it may be difficult to secure the unique physical properties required by the hollow metal nanoparticles. For example, when hollow metal nanoparticles outside the above range are used as a catalyst of a fuel cell, the effect of improving the efficiency of the fuel cell may be somewhat insufficient.
  • the forming of the hollow metal nanoparticles by mixing the solution and the reducing agent may be performed at a temperature in a range of 4 ° C. or more and less than 100 ° C.
  • the temperature may be performed at a temperature of 4 ° C. or higher and 80 ° C. or lower. Since it can be manufactured at a low temperature of less than 100 °C, the manufacturing method is simple, there is an advantage in the process, the cost reduction effect is large.
  • FIGS. 1, 4, and 5 show transmission electron microscope (TEM) images of hollow metal nanoparticles prepared according to Experimental Examples 1, 4, and 5, respectively.
  • the nanoparticles of FIGS. 1, 4, and 5 are manufactured at temperature conditions of 14 ° C., 25 ° C., and 60 ° C., respectively, and it can be seen that hollows are uniformly formed at all of the temperature conditions.
  • Forming the hollow metal nanoparticles in one embodiment of the present application may be performed for 5 minutes to 120 minutes, more specifically 10 minutes to 90 minutes, even more specifically 20 minutes to 60 minutes.
  • the step of centrifuging the solution containing the hollow metal nanoparticles to precipitate the hollow metal nanoparticles contained in the solution may further include. Only the hollow metal nanoparticles separated after centrifugation can be recovered. If necessary, the step of firing the hollow metal nanoparticles may be additionally performed.
  • hollow metal nanoparticles having a uniform size in several nano-sizes may be manufactured.
  • the conventional method not only it was difficult to manufacture the nano metal hollow metal nanoparticles, but also it was more difficult to produce a uniform size, while according to the manufacturing method of the present application, the uniform hollow metal nanoparticles of several nanometers in size There is an advantage that can be manufactured simply.
  • the average particle diameter of the hollow metal nanoparticles prepared according to one embodiment of the present application may be 30 nanometers or less, 20 nanometers or less, 10 nanometers or less, and 6 nanometers or less. It may also be 1 nanometer or more.
  • the thickness of the shell portion may be greater than 0 nanometers and 5 nanometers or less, greater than 0 nanometers and 3 nanometers or less, and greater than 0 nanometers and 1 nanometer or less.
  • hollow metal nanoparticles having an average particle diameter of less than 1 nanometer, and when the particle diameter of the hollow metal nanoparticles is 30 nanometer or less, the nanoparticles may be used in various fields.
  • the advantage is great.
  • the particle diameter of a hollow metal nanoparticle is 20 nanometers or less, when it is 10 nanometers or less, when it is 6 nanometers or less, it is more preferable. If the formed hollow metal nanoparticles are used, for example, as a catalyst for a fuel cell, the efficiency of the fuel cell can be significantly increased.
  • One embodiment of the present application provides a hollow metal nanoparticles produced by the above production method.
  • Hollow metal nanoparticles according to one embodiment of the present application may be a spherical shape.
  • Hollow metal nanoparticles according to an embodiment of the present application is a hollow core (core); And at least one shell including the first metal and / or the second metal.
  • the shell may be present in at least one region of the hollow exterior, or may be present in the front surface of the hollow exterior. If the shell is present in some areas outside the hollow, it may be present in the form of discontinuous faces.
  • the shell may be a single layer or two or more layers.
  • the first metal and the second metal may be present in a mixed form. At this time, it may be mixed uniformly or heterogeneously.
  • the atomic percentage ratio of the first metal and the second metal may be 1: 5 to 10: 1.
  • the first metal and the second metal may exist in a gradation state in the shell, and the portion of the shell contacting the hollow core is 50 vol% or more. Or, at least 70% by volume, and at least 50% by volume, or at least 70% by volume, of the second metal may be present in the surface portion of the shell in contact with the outside.
  • the shell when the shell is a single layer, the shell may include only the first metal or the second metal.
  • the shell may be formed in at least one region in a porous form.
  • the shell may include only the first metal or the second metal, or may include the first metal and the second metal together.
  • the porosity of the shell may be 20% by volume or less, 10% by volume or less.
  • Hollow metal nanoparticles according to an embodiment of the present application is a hollow core; One or more first shells comprising a first metal; And one or more second shells comprising a second metal.
  • the first shell may be present in at least one region of the hollow exterior and may be present in the front surface. If the first shell is present in some areas outside the hollow may be present in the form of discontinuous face.
  • the second shell may be present in at least one region of the outer surface of the first shell and may exist in a form surrounding the front surface of the outer surface of the first shell. If the second shell is present in some region of the outer surface of the first shell it may be present in the form of discontinuous faces.
  • the hollow metal nanoparticle includes a hollow core, a first shell in which a second metal ion having a negative charge is present in at least one region outside the hollow, and a first shell having a first metal ion having a positive charge again. And a second shell present in at least one region of the outer surface of the.
  • the hollow metal nanoparticle may include a hollow core, a first shell in which first metal ions having positive charges exist in at least one region outside the hollow, and a second shell of second metal ions having negative charges again. And a second shell present in at least one region of the outer surface of the.
  • the hollow metal nanoparticles prepared by the manufacturing method according to an exemplary embodiment of the present application may generally be used in place of the existing nanoparticles in the field in which the nanoparticles may be used. Since the hollow metal nanoparticles of the present application are very small in size and have a larger specific surface area than the conventional nanoparticles, the hollow metal nanoparticles may exhibit excellent activity as compared to the conventional nanoparticles. Specifically, the hollow metal nanoparticles prepared according to the manufacturing method of the present application may be used in various fields such as a catalyst, a drug delivery, a gas sensor, and the like. The hollow metal nanoparticles may be used as active substance preparations in cosmetics, pesticides, animal nutrition or food supplements as catalysts, and may be used as pigments in electronics, optical articles or polymers.
  • Figure 1 shows a transmission electron microscope (TEM) image of the hollow metal nanoparticles prepared according to Experimental Example 1.
  • the particle diameter of the hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of FIG. 1 was about 5 nm.
  • the particle diameters of the formed hollow metal nanoparticles were measured for 200 or more hollow metal nanoparticles using graphic software (MAC-View) based on FIG. 1, and the average particle diameter obtained through the obtained statistical distribution was 5 nm.
  • Hollow metal nanoparticles were prepared in the same manner as Experimental Example 1, except that the addition rate of the reducing agent was 100 ml / h.
  • Figure 2 shows a transmission electron microscope (TEM) image of the hollow metal nanoparticles prepared according to Experimental Example 2.
  • the particle diameter of the hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of FIG. 2 is approximately It was about 16 nm.
  • the particle diameters of the formed hollow metal nanoparticles were measured for 200 or more hollow metal nanoparticles using graphic software (MAC-View) based on FIG. 2, and the average particle diameter obtained through the obtained statistical distribution was 16 nm.
  • Hollow metal nanoparticles were prepared in the same manner as Experimental Example 1, except that the addition rate of the reducing agent was 0.1 ml / h.
  • Figure 3 shows a transmission electron microscope (TEM) image of the metal nanoparticles prepared according to Experimental Example 3.
  • the particle diameter of the hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of FIG. 3 was about 12 nm.
  • the particle diameters of the formed metal nanoparticles were measured for 200 or more hollow metal nanoparticles using graphic software (MAC-View) based on FIG. 3, and the average particle diameter obtained through the obtained statistical distribution was 12 nm.
  • the addition rate of the reducing agent is more preferably more than 0.1 ml / h.
  • Hollow metal nanoparticles were prepared in the same manner as in Experiment 1, except that the temperature was performed at 25 ° C.
  • Figure 4 shows a transmission electron microscope (TEM) image of the hollow metal nanoparticles prepared according to Experimental Example 4.
  • the particle diameter of the hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of FIG. 4 was about 17 nm.
  • the particle diameters of the formed hollow metal nanoparticles were measured for 200 or more hollow metal nanoparticles using graphic software (MAC-View) based on FIG. 4, and the average particle diameter obtained through the obtained statistical distribution was 17 nm.
  • Hollow metal nanoparticles were prepared in the same manner as in Experiment 1, except that the reaction was carried out at a temperature of 60 ° C.
  • Figure 5 shows a transmission electron microscope (TEM) image of the hollow metal nanoparticles prepared according to Experimental Example 5.
  • the particle diameter of the hollow metal nanoparticles obtained by the Scherrer equation calculation method for HR-TEM of FIG. 5 was about 13 nm.
  • the particle diameters of the formed hollow metal nanoparticles were measured for 200 or more hollow metal nanoparticles using graphic software (MAC-View) based on FIG. 5, and the average particle diameter obtained through the obtained statistical distribution was 13 nm.
  • most of the nanoparticles are not hollow, and are synthesized by agglomerating into amorphous particles.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

La présente invention concerne un procédé de fabrication de nanoparticules métalliques creuses et des nanoparticules métalliques fabriquées ainsi, et plus spécifiquement un procédé de fabrication de nanoparticules métalliques creuses comprenant les étapes suivantes : préparation d'une solution comprenant un premier sel métallique, un second sel métallique, un agent de stabilisation, et un solvant ; et formation de nanoparticules métalliques creuses par mélange de la solution et d'un agent réducteur. Les nanoparticules métalliques creuses fabriquées selon le procédé de fabrication de la présente invention possèdent une très petite taille et une plus grande surface spécifique que des nanoparticules classiques ; elles peuvent ainsi présenter une activité supérieure aux nanoparticules classiques et être utilisées dans divers domaines, par exemple pour un support d'administration de médicaments et un capteur de gaz.
PCT/KR2015/005969 2014-06-13 2015-06-12 Procédé de fabrication de nanoparticules métalliques creuses, et nanoparticules métalliques creuses fabriquées ainsi Ceased WO2015190888A1 (fr)

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CN108356279B (zh) * 2018-03-09 2019-05-14 华中科技大学 一种空心金纳米材料的制备方法
CN110907428B (zh) * 2019-12-19 2022-12-27 哈尔滨工业大学 还原诱导法制备可重复利用的多孔sers金属基底的方法及其应用
CN112121061A (zh) * 2020-09-21 2020-12-25 重庆医科大学 一种多功能中空铈纳米颗粒及中空铈纳米复合物载药体系的构建和应用
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