WO2014114828A1 - Method for obtaining silver nanostructures and nanostructures produced by means of said method - Google Patents

Method for obtaining silver nanostructures and nanostructures produced by means of said method Download PDF

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Publication number
WO2014114828A1
WO2014114828A1 PCT/ES2014/070003 ES2014070003W WO2014114828A1 WO 2014114828 A1 WO2014114828 A1 WO 2014114828A1 ES 2014070003 W ES2014070003 W ES 2014070003W WO 2014114828 A1 WO2014114828 A1 WO 2014114828A1
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Prior art keywords
nanostructures
solution
ethylene glycol
silver
procedure
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PCT/ES2014/070003
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Spanish (es)
French (fr)
Inventor
María Fe MENÉNDEZ SUÁREZ
David GÓMEZ PLAZA
Bernardino RUIZ GONZÁLEZ
Luis José ANDRÉS MENÉNDEZ
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Fundacion Itma
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G5/00—Compounds of silver
    • 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
    • B22F1/0547—Nanofibres or nanotubes
    • 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
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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

Definitions

  • the present invention is encompassed in the field of nanotechnology, referring to a process for obtaining silver nanostructures, as well as to
  • the method of the invention makes it possible to obtain nanowires and closed nanostructures, mainly nano-rings and other structures of polygonal shape or of combined polygonal and ring forms, with a high yield and in a very short time interval, resulting, by example in the case of wire-shaped structures, large nanowires
  • the polyvinylpyrrolidone polymer is one of the most widely used metal nanoparticle stabilizing agents, in particular in the synthesis of silver nanoparticles.
  • PVP polyvinylpyrrolidone polymer
  • one of the first syntheses was based on the photoreduction of AgNO 3 in the presence of PVP as a stabilizing agent using a UV radiation of 243 nm.
  • Silver nanoparticles between 15 and 22 nm are obtained with this method, depending on the molar ratio between AgNO 3 and PVP (HH Huang, XP Ni, GL Loy, CH Chew, KL Tan, FC Loh, JF Deng, GQ Xu , Langmuir, 1996, 12, 909-912).
  • PVP acts as a stabilizing agent for silver nanoparticles
  • nanostructures of different forms for example nanowires and nanoparticles, which imply small yields for each nanostructure
  • WO 2011/031483 A2 describes a method for preparing metal nanowires comprising providing a first reaction mixture by combining a polyol, a stabilizer and an ionic additive in a first
  • reaction vessel purge this first reaction mixture with an inert gas, combine it with a metal salt and carry out the reduction of the metal.
  • EP 2147733 A1 relates to a method for obtaining silver-containing nanostructures wherein a polymeric compound containing a
  • an object of the present invention is to provide a method for obtaining silver nanostructures, in particular nanowires and closed nanostructures, mainly nanorings and other structures of polygonal shape or of polygonal and ring combined form, with a high performance and in a very short time interval, resulting, for example in the case of wire-shaped structures, large nanowires
  • the object of the invention are the nanostructures obtained by said process, as well as their use.
  • Figures 1A and IB are FESEM images of the silver nanowires obtained according to an embodiment of the method of the invention.
  • Figure 2 is a FESEM image of the
  • Silver nanorings obtained according to another embodiment of the method of the invention.
  • Figure 3 is a FESEM image of
  • Figure 4 is a FESEM image of closed polygonal shaped silver and ring nanostructures obtained according to another embodiment of the method of the invention.
  • Solution C ethylene glycol
  • Solution A ethylene glycol containing AgNO 3
  • Solution D optionally KBr
  • reaction is maintained until turbidity appears, becomes more viscous, pearly and / or acquires a grayish color, which indicates the presence of
  • reaction product is homogenized and centrifuged obtained, disregarding the supernatant;
  • the nanostructures are suspended in a suitable solvent for their conservation.
  • the concentration of the solutions used in the different steps of the process of the invention are the following:
  • Solution A 0.12-0.52 g of AgNO 3 in 20 ml of ethylene glycol;
  • Solution B 0.15-0.45 g of PVP360 in 20 ml of ethylene glycol;
  • Solution C 0.0068-0.0300 g of CuCl 2 in 10 ml of ethylene glycol
  • Solution D 0.010-0.014 g of KBr in 10 ml of ethylene glycol.
  • step i) the previously heated ethylene glycol is maintained at a temperature of 160-180 ° C for about 30 minutes before the addition of Solution C, in particular 0.4-1.6 ml of Solution C and, after the addition of said Solution C, this
  • step ii) the peristaltic pump operates at a flow rate of 1.5 ml / min. Also, preferably in step iii) the reaction time is maintained for 15-90 minutes.
  • the preferred diluent for use in step iv) is acetone.
  • the preferred solvent for the dispersion and preservation of the nanostructures in step v) is absolute ethanol.
  • step ii) 15 ml of Solution A and 15 ml of
  • step ii) 15 ml of the
  • the reaction is maintained for 15 minutes, during which the solution becomes noticeably more viscous, pearly and grayish, changes that are due to the presence of nanowires. At this time, the reaction is terminated. The performance of the reaction is superior to
  • the reaction product consists mainly of silver nanowires with a diameter between 100 and 300 nm and a length of 100 to 150 ⁇ m (see Figure 1).
  • Example 2 Obtaining closed silver nanostructures
  • the yield of the reaction is greater than 40% for closed silver nanostructures with a perimeter between 30 and 100 microns,

Abstract

The invention relates to a method for producing silver nanostructures, especially nanowires and closed nanostructures, mainly nanorings and other structures having a polygonal shape or a combined polygonal and ring shape, using a solution of copper (II) chloride in ethylene glycol, PVP in ethylene glycol and AgNO3, optionally together with KBr, resulting in a high yield regarding the production of such silver nanostructures and in very short periods of time.

Description

PROCEDIMIENTO PARA LA OBTENCIÓN DE NANOESTRUCTURAS DE PLATA Y NANOESTRUCTURAS OBTENIDAS MEDIANTE DICHO PROCEDURE FOR THE OBTAINING OF SILVER NANOSTRUCTURES AND NANOSTRUCTURES OBTAINED THROUGH SAID
PROCEDIMIENTO CAMPO TÉCNICO DE LA INVENCIÓN PROCEDURE TECHNICAL FIELD OF THE INVENTION
La presente invención se engloba en el campo de la nanotecnologia, refiriéndose a un procedimiento para obtener nanoestructuras de plata, asi como a las The present invention is encompassed in the field of nanotechnology, referring to a process for obtaining silver nanostructures, as well as to
nanoestructuras obtenidas mediante tal procedimiento. Más particularmente, el procedimiento de la invención permite obtener nanohilos y nanoestructuras cerradas, principalmente nanoanillos y otras estructuras de forma poligonal o de forma combinada poligonal y de anillo, con un alto rendimiento y en un intervalo de tiempo muy corto, dando como resultado, por ejemplo en el caso de estructuras en forma de hilo, nanohilos de gran nanostructures obtained by such procedure. More particularly, the method of the invention makes it possible to obtain nanowires and closed nanostructures, mainly nano-rings and other structures of polygonal shape or of combined polygonal and ring forms, with a high yield and in a very short time interval, resulting, by example in the case of wire-shaped structures, large nanowires
longitud, por ejemplo de 100-150 mieras, en un intervalo de tiempo muy corto, de entre 15 y 20 minutos. length, for example 100-150 microns, in a very short time interval, between 15 and 20 minutes.
ANTECEDENTES DE LA INVENCIÓN BACKGROUND OF THE INVENTION
Son conocidos diversos procedimientos para la preparación de nanoestructuras de plata, donde, en general, la síntesis de nanopartículas metálicas en disolución se lleva a cabo mediante el empleo de un precursor metálico, un agente reductor y un agente estabilizante. En particular, el mecanismo de formación de disoluciones coloidales a partir de la reducción de iones plata consta de dos etapas diferentes: nucleación y crecimiento. El proceso de nucleación requiere una alta energía de activación, mientras que el proceso de crecimiento requiere una baja energía de activación. El tamaño y la forma de las nanopartículas obtenidas dependerá de las velocidades relativas de estos procesos que pueden ser controladas a través de la modificación de los parámetros de reacción (concentración, Various methods for the preparation of silver nanostructures are known, where, in general, the synthesis of metal nanoparticles in solution is carried out by the use of a metal precursor, a reducing agent and a stabilizing agent. In particular, the mechanism of formation of colloidal solutions from the reduction of silver ions consists of two different stages: nucleation and growth. The nucleation process requires a high activation energy, while the growth process requires a low activation energy. The size and shape of the nanoparticles obtained will depend on the relative speeds of these processes that can be controlled through the modification of the reaction parameters (concentration,
temperatura, pH, poder reductor, etc.) (C. Burda, X. temperature, pH, reducing power, etc.) (C. Burda, X.
Chen, R. Narayanan, M . A. El-Sayed, Chem. Rev., 2005, 105, 1025-1102; B.L. Cushing, V.L. Koleschineko , C.J.Chen, R. Narayanan, M. A. El-Sayed, Chem. Rev., 2005, 105, 1025-1102; B.L. Cushing, V.L. Koleschineko, C.J.
O'Connor, Chem. Rev. 2004, 104, 3893-3946; D.D. Evanoff, Jr., G. Chumanov, ChemPhysChem, 2005, 6, 1221-1231) . O'Connor, Chem. Rev. 2004, 104, 3893-3946; D.D. Evanoff, Jr., G. Chumanov, ChemPhysChem, 2005, 6, 1221-1231).
El polímero polivinilpirrolidona (PVP) es uno de los agentes estabilizantes de nanopartículas metálicas más ampliamente usados, en particular en la síntesis de nanopartículas de plata. Así, una de las primeras síntesis se basaba en la fotoreducción de AgNO3 en presencia de PVP como agente estabilizante empleando una radiación UV de 243 nm. Con este método se obtienen nanopartículas de plata de entre 15 y 22 nm, en función de la relación molar entre AgNO3 y PVP (H.H. Huang, X.P. Ni, G.L. Loy, C.H. Chew, K.L. Tan, F.C. Loh, J.F. Deng, G.Q. Xu, Langmuir, 1996, 12, 909-912) . También son conocidos diferentes métodos donde la PVP actúa como agente estabilizante de nanopartículas de plata The polyvinylpyrrolidone polymer (PVP) is one of the most widely used metal nanoparticle stabilizing agents, in particular in the synthesis of silver nanoparticles. Thus, one of the first syntheses was based on the photoreduction of AgNO 3 in the presence of PVP as a stabilizing agent using a UV radiation of 243 nm. Silver nanoparticles between 15 and 22 nm are obtained with this method, depending on the molar ratio between AgNO 3 and PVP (HH Huang, XP Ni, GL Loy, CH Chew, KL Tan, FC Loh, JF Deng, GQ Xu , Langmuir, 1996, 12, 909-912). Different methods are also known where PVP acts as a stabilizing agent for silver nanoparticles
sintetizadas mediante reducción de sales de plata con distintos agentes reductores químicos, tales como bitartrato potásico (Y. Tan, X. Dai, Y. Li, D. Zhu, J. Mater. Chem., 2003, 13, 1069-1075) o DMF (I. Pastoriza- Santos, L.M. Liz-Marzán, Langmuir, 2002, 18, 2888-2894) e incluso empleando microondas y el propio PVP como agente reductor (R. He, X. Qian, J. Yin, Z. Zhu, J. synthesized by reducing silver salts with various chemical reducing agents, such as potassium bitartrate (Y. Tan, X. Dai, Y. Li, D. Zhu, J. Mater.Chem., 2003, 13, 1069-1075) or DMF (I. Pastoriza-Santos, LM Liz-Marzán, Langmuir, 2002, 18, 2888-2894) and even using microwaves and the PVP itself as a reducing agent (R. He, X. Qian, J. Yin, Z. Zhu , J.
Mater. Chem., 2002, 12, 3783-3786) . También se ha empleado PVP como estabilizante en reacciones de Mater. Chem., 2002, 12, 3783-3786). PVP has also been used as a stabilizer in reactions of
reducción de AgNO3 con polioles según el llamado "método poliol", que conduce a la síntesis de nanoesferas, nanocubos, nanobarras o nanocables de plata. En general, el estudio de los parámetros que afectan a las reduction of AgNO 3 with polyols according to the so-called "polyol method", which leads to the synthesis of nanospheres, nanocubes, nanobars or silver nanowires. In general, the study of the parameters that affect the
reacciones y, en especial, la concentración del polímero estabilizante, permite ejercer un gran control sobre el tamaño y la forma de las nanoparticulas de plata (Y. Sun, Y. Xia, Adv. Mat . , 2002, 14, 833-837. f) B. Wiley, Y. Sun, B. Mayers, Y. Xia, Chem. Eur . J., 2005, 11, 454- 463) . reactions and, especially, the concentration of the polymer stabilizer, allows to exercise great control over the size and shape of silver nanoparticles (Y. Sun, Y. Xia, Adv. Mat., 2002, 14, 833-837. f) B. Wiley, Y. Sun, B. Mayers, Y. Xia, Chem. Eur. J., 2005, 11, 454-463).
El principal problema de estos métodos conocidos para la producción de nanoestructuras es que se The main problem with these known methods for the production of nanostructures is that they
obtienen mezclas de nanoestructuras de distintas formas, por ejemplo nanohilos y nanoparticulas, que implican rendimientos pequeños para cada nanoestructura they obtain mixtures of nanostructures of different forms, for example nanowires and nanoparticles, which imply small yields for each nanostructure
particular, además de costosos pasos de separación posterior . Con el fin de solucionar estos problemas, por ejemplo la WO 2011/031483 A2 describe un método para preparar nanohilos metálicos que comprende proporcionar una primera mezcla de reacción combinando un poliol, un estabilizante y un aditivo iónico en un primer particular, in addition to costly subsequent separation steps. In order to solve these problems, for example WO 2011/031483 A2 describes a method for preparing metal nanowires comprising providing a first reaction mixture by combining a polyol, a stabilizer and an ionic additive in a first
recipiente de reacción, purgar esta primera mezcla de reacción con un gas inerte, combinarla con una sal metálica y llevar a cabo la reducción del metal. reaction vessel, purge this first reaction mixture with an inert gas, combine it with a metal salt and carry out the reduction of the metal.
La EP 2147733 A1 se refiere a un método para obtener nanoestructuras que contienen plata donde se dispersa un compuesto polimérico que contiene un EP 2147733 A1 relates to a method for obtaining silver-containing nanostructures wherein a polymeric compound containing a
segmento hidrofilico enlazado a una cadena hydrophilic segment linked to a chain
polialquilenimina en un medio, se añade entonces óxido de plata y se lleva a cabo una reducción. polyalkyleneimine in a medium, then silver oxide is added and a reduction is carried out.
Por tanto, sigue existiendo la necesidad de disponer de un procedimiento para la obtención Therefore, there remains a need to have a procedure for obtaining
especifica de nanoestructuras de plata, donde se puedan controlar sus formas y tamaños y que permita obtener tales nanoestructuras, en particular nanohilos y nanoanillos, de forma reproducible, con un tamaño adecuado y un alto rendimiento. specifies silver nanostructures, where their shapes and sizes can be controlled and which allows obtaining such nanostructures, in particular nanowires and nano-rings, reproducibly, with an adequate size and high performance.
DESCRIPCION DE LA INVENCION DESCRIPTION OF THE INVENTION
A la vista de lo anteriormente enunciado, un objeto de la presente invención es proporcionar un procedimiento para obtener nanoestructuras de plata, en particular nanohilos y nanoestructuras cerradas, principalmente nanoanillos y otras estructuras de forma poligonal o de forma combinada poligonal y de anillo, con un alto rendimiento y en un intervalo de tiempo muy corto, dando como resultado, por ejemplo en el caso de estructuras en forma de hilo, nanohilos de gran In view of the above, an object of the present invention is to provide a method for obtaining silver nanostructures, in particular nanowires and closed nanostructures, mainly nanorings and other structures of polygonal shape or of polygonal and ring combined form, with a high performance and in a very short time interval, resulting, for example in the case of wire-shaped structures, large nanowires
longitud, por ejemplo de 100-150 mieras, en un intervalo de tiempo muy corto, de entre 15 y 20 minutos. Son igualmente objeto de la invención las nanoestructuras obtenidas mediante dicho procedimiento, asi como su utilización . length, for example 100-150 microns, in a very short time interval, between 15 and 20 minutes. Also the object of the invention are the nanostructures obtained by said process, as well as their use.
BREVE DESCRIPCIÓN DE LAS FIGURAS BRIEF DESCRIPTION OF THE FIGURES
Las figuras 1A y IB son imágenes FESEM de los nanohilos de plata obtenidos según una realización del procedimiento de la invención. Figures 1A and IB are FESEM images of the silver nanowires obtained according to an embodiment of the method of the invention.
La figura 2 es una imagen FESEM de los Figure 2 is a FESEM image of the
nanoanillos de plata obtenidos según otra realización del procedimiento de la invención. Silver nanorings obtained according to another embodiment of the method of the invention.
La figura 3 es una imagen FESEM de Figure 3 is a FESEM image of
nanoestructuras de plata cerradas de forma poligonal obtenidas según otra realización del procedimiento de la invención . La figura 4 es una imagen FESEM de nanoestructuras de plata cerradas de forma poligonal y anillo combinadas obtenidas según otra realización del procedimiento de la invención. polygonally closed silver nanostructures obtained according to another embodiment of the method of the invention. Figure 4 is a FESEM image of closed polygonal shaped silver and ring nanostructures obtained according to another embodiment of the method of the invention.
EXPOSICIÓN DETALLADA DE LA REALIZACIÓN PREFERENTE DE LA INVENCIÓN DETAILED EXHIBITION OF THE PREFERRED EMBODIMENT OF THE INVENTION
El procedimiento de la invención para obtener nanoestructuras de plata, en particular nanohilos y nanoestructuras cerradas, principalmente nanoanillos y otras estructuras de forma poligonal o de forma The process of the invention for obtaining silver nanostructures, in particular nanowires and closed nanostructures, mainly nano-rings and other polygonal or shaped structures
combinada poligonal y de anillo, comprende las etapas de: combined polygonal and ring, comprises the steps of:
i) en un recipiente que contiene 50 mi de etilenglicol , bajo reflujo, caliente y con agitación, se incorpora una disolución de cloruro de cobre (II) en etilenglicol (en adelante Disolución C) , manteniendo la temperatura y la agitación;  i) in a vessel containing 50 ml of ethylene glycol, under reflux, hot and with stirring, a solution of copper (II) chloride is incorporated in ethylene glycol (hereinafter Solution C), maintaining the temperature and stirring;
ii) al recipiente se añaden unas gotas de una disolución de polivinilpirrolidona PVP360 en  ii) add a few drops of a solution of polyvinylpyrrolidone PVP360 to the container
etilenglicol (en adelante Disolución B) y ethylene glycol (hereinafter Solution B) and
simultáneamente, mediante bomba peristáltica de dos canales, por uno de ellos se adiciona una disolución en etilenglicol conteniendo AgNO3 (en adelante Disolución A) y opcionalmente KBr (en adelante Disolución D) y por el otro canal la Disolución B, seguida de una adición final de unas gotas de Disolución B; simultaneously, by means of a two-channel peristaltic pump, one of them is added a solution in ethylene glycol containing AgNO 3 (hereinafter Solution A) and optionally KBr (hereinafter Solution D) and through the other channel Solution B, followed by an addition end of a few drops of Solution B;
iii)la reacción se mantiene hasta que aparece turbidez, se vuelve más viscosa, nacarada y/o adquiere un color grisáceo, lo que indica la presencia de  iii) the reaction is maintained until turbidity appears, becomes more viscous, pearly and / or acquires a grayish color, which indicates the presence of
nanoestructuras de plata; silver nanostructures;
iv) se diluye con un diluyente adecuado, se homogeneiza y centrifuga el producto de reacción obtenido, despreciando el sobrenadante; las iv) is diluted with a suitable diluent, the reaction product is homogenized and centrifuged obtained, disregarding the supernatant; the
nanoestructuras sólidas recuperadas se lavan recovered solid nanostructures are washed
sucesivamente con el diluyente empleado y con etanol; successively with the diluent used and with ethanol;
v) finalmente, las nanoestructuras se suspenden en un disolvente adecuado para su conservación.  v) finally, the nanostructures are suspended in a suitable solvent for their conservation.
Preferentemente, la concentración de las disoluciones empleadas en los diferentes pasos del procedimiento de la invención son las siguientes: Preferably, the concentration of the solutions used in the different steps of the process of the invention are the following:
Disolución A: 0,12-0,52 g de AgNO3 en 20 mi de etilenglicol ; Solution A: 0.12-0.52 g of AgNO 3 in 20 ml of ethylene glycol;
Disolución B: 0,15-0,45 g de PVP360 en 20 mi de etilenglicol ;  Solution B: 0.15-0.45 g of PVP360 in 20 ml of ethylene glycol;
Disolución C: 0,0068-0,0300 g de CuCl2 en 10 mi de etilenglicol; Solution C: 0.0068-0.0300 g of CuCl 2 in 10 ml of ethylene glycol;
Disolución D: 0,010-0,014 g de KBr en 10 mi de etilenglicol .  Solution D: 0.010-0.014 g of KBr in 10 ml of ethylene glycol.
También de forma preferente, en la etapa i) el etilenglicol previamente calentado se mantiene a una temperatura de 160 - 180°C durante aproximadamente 30 minutos antes de la adición de la Disolución C, en particular de 0,4-1,6 mi de la Disolución C y, tras la adición de dicha Disolución C, se mantiene esta Also preferably, in step i) the previously heated ethylene glycol is maintained at a temperature of 160-180 ° C for about 30 minutes before the addition of Solution C, in particular 0.4-1.6 ml of Solution C and, after the addition of said Solution C, this
temperatura y la agitación durante aproximadamente 15 minutos . temperature and stirring for approximately 15 minutes.
De forma igualmente preferente, en la etapa ii), la bomba peristáltica opera a un caudal de 1,5 ml/min. Asimismo, preferentemente en la etapa iii) el tiempo de reacción se mantiene durante 15-90 minutos. Similarly, in step ii), the peristaltic pump operates at a flow rate of 1.5 ml / min. Also, preferably in step iii) the reaction time is maintained for 15-90 minutes.
El diluyente preferente para su uso en la etapa iv) es acetona. El disolvente preferente para la dispersión y conservación de las nanoestructuras en la etapa v) es el etanol absoluto. En una forma de realización del procedimiento de la invención, en particular para la obtención The preferred diluent for use in step iv) is acetone. The preferred solvent for the dispersion and preservation of the nanostructures in step v) is absolute ethanol. In an embodiment of the method of the invention, in particular for obtaining
esencialmente de nanohilos de plata, en la etapa ii) se adicionan 15 mi de la Disolución A y 15 mi de la essentially from silver nanowires, in step ii) 15 ml of Solution A and 15 ml of
Disolución B. Dissolution B.
En otra forma de realización del procedimiento de la invención, en particular para la obtención In another embodiment of the method of the invention, in particular for obtaining
esencialmente de nanoestructuras cerradas y nanoanillos de plata, en la etapa ii) se adicionan 15 mi de la essentially of closed nanostructures and silver nano-rings, in step ii) 15 ml of the
Disolución B y 15 mi de una mezcla formada por la Solution B and 15 ml of a mixture formed by the
Disolución A y la Disolución D. Dissolution A and Dissolution D.
El rendimiento del procedimiento de la invención es muy superior al de los procedimientos ya conocidos, alcanzando valores de entre el 40 y el 95% para las nanoestructuras resultantes, las cuales tienen un tamaño también mayor, siendo por ello muy ventajosas en cuanto a su aplicación, por ejemplo para revestimientos The performance of the process of the invention is much higher than that of the known processes, reaching values of between 40 and 95% for the resulting nanostructures, which are also of a larger size, and are therefore very advantageous in their application , for example for coatings
transparentes y conductores destinados a pantallas transparentes conductoras, células fotovoltaicas de capa fina, etc. transparent and conductors for transparent conductive screens, thin-film photovoltaic cells, etc.
EJEMPLOS Ejemplo 1: Obtención de nanohilos de plata EXAMPLES Example 1: Obtaining silver nanowires
En un matraz se introducen 50 mi de Into a flask, 50 ml of
etilenglicol , bajo reflujo, en baño de aceite y con agitación, y se mantienen a 170°C durante 30 minutos. Se incorporan al matraz 0,4 mi de la Disolución C, manteniendo las condiciones de temperatura y agitación durante 15 minutos. Entonces se añaden al matraz 6 gotas de la Disolución B y simultáneamente, mediante una bomba peristáltica y a un caudal de 1,5 ml/min, 15 mi de la Disolución A y 15 mi de la Disolución B. Por último se añaden 6 gotas de la Disolución B. ethylene glycol, under reflux, in an oil bath and with stirring, and kept at 170 ° C for 30 minutes. 0.4 ml of Solution C is added to the flask, maintaining the conditions of temperature and agitation during 15 minutes. Then 6 drops of Solution B are added to the flask and simultaneously, by means of a peristaltic pump and at a flow rate of 1.5 ml / min, 15 ml of Solution A and 15 ml of Solution B. Finally, 6 drops of solution are added. Dissolution B.
Finalizada la incorporación de reactivos, se mantiene la reacción durante 15 minutos, tiempo en el cual la disolución se vuelve sensiblemente más viscosa, nacarada y de color grisáceo, cambios que se deben a la presencia de nanohilos. En este momento, la reacción se da por terminada. El rendimiento de la reacción es superior alAfter the incorporation of reagents, the reaction is maintained for 15 minutes, during which the solution becomes noticeably more viscous, pearly and grayish, changes that are due to the presence of nanowires. At this time, the reaction is terminated. The performance of the reaction is superior to
95%. El producto de reacción consiste mayoritariamente en nanohilos de plata con un diámetro comprendido entre 100 y 300 nm y una longitud de 100 a 150 μm (véase la Figura 1 ) . 95%. The reaction product consists mainly of silver nanowires with a diameter between 100 and 300 nm and a length of 100 to 150 μm (see Figure 1).
Ejemplo 2: Obtención de nanoestructuras cerradas de plata Example 2: Obtaining closed silver nanostructures
En un matraz se introducen 50 mi de Into a flask, 50 ml of
etilenglicol , bajo reflujo, en baño de aceite y con agitación, y se mantienen a 170°C durante 30 minutos. Se incorporan al matraz 0,4 mi de la Disolución C, ethylene glycol, under reflux, in an oil bath and with stirring, and kept at 170 ° C for 30 minutes. 0.4 ml of Solution C is added to the flask,
manteniendo las condiciones de temperatura y agitación durante 15 minutos. Entonces se añaden al matraz 6 gotas de la Disolución B y simultáneamente, mediante una bomba peristáltica a un caudal de 1,5 ml/min, 15 mi de la Disolución B y 15 mi de una mezcla de las Disoluciones A y D. Por último se añaden 6 gotas de la Disolución B. Finalizada la incorporación de reactivos, se mantiene la reacción durante 30 minutos, tiempo en el cual la disolución adquiere gran turbidez, observándose una gran turbulencia en el interior del matraz. La disolución se vuelve sensiblemente más viscosa, de color grisáceo y con visos nacarados, cambios que se deben a la presencia de nanoestructuras cerradas. En este momento, la reacción se da por terminada. maintaining the conditions of temperature and agitation during 15 minutes. Then 6 drops of Solution B are added to the flask and simultaneously, by means of a peristaltic pump at a flow rate of 1.5 ml / min, 15 ml of Solution B and 15 ml of a mixture of Solutions A and D. Finally 6 drops of Solution B are added. Once the reagents have been added, the The reaction is maintained for 30 minutes, during which time the solution acquires great turbidity, with great turbulence observed inside the flask. The solution becomes noticeably more viscous, grayish and pearly, changes that are due to the presence of closed nanostructures. At this time, the reaction is terminated.
El rendimiento de la reacción es superior al 40% para las nanoestructuras cerradas de plata con un perímetro comprendido entre 30 y 100 mieras, The yield of the reaction is greater than 40% for closed silver nanostructures with a perimeter between 30 and 100 microns,
correspondiendo el resto a nanoestructuras abiertas (véase la Figura 2) . the rest corresponding to open nanostructures (see Figure 2).

Claims

REIVINDICACIONES
1. -Procedimiento para la obtención de 1. -Procedure to obtain
nanoestructuras de plata, caracterizado por que silver nanostructures, characterized by
comprende las etapas de: it includes the stages of:
i) en un recipiente que contiene 50 mi de etilenglicol , bajo reflujo, caliente y con agitación, se incorpora una disolución de cloruro de cobre (II) en etilenglicol, manteniendo la temperatura y la agitación;  i) in a vessel containing 50 ml of ethylene glycol, under reflux, hot and with stirring, a solution of copper (II) chloride is incorporated in ethylene glycol, maintaining the temperature and stirring;
ii) al recipiente se añaden unas gotas de una disolución de polivinilpirrolidona PVP360 en  ii) add a few drops of a solution of polyvinylpyrrolidone PVP360 to the container
etilenglicol y simultáneamente, mediante bomba ethylene glycol and simultaneously, by pump
peristáltica, se adicionan una disolución en peristaltic, a solution is added in
etilenglicol conteniendo AgNO3, y opcionalmente KBr, y una disolución de PVP360 en etilenglicol, seguida de una adición final de unas gotas de PVP360; ethylene glycol containing AgNO 3 , and optionally KBr, and a solution of PVP360 in ethylene glycol, followed by a final addition of a few drops of PVP360;
iii) la reacción se mantiene hasta que aparece turbidez, se vuelve más viscosa, nacarada y/o adquiere un color grisáceo, lo que indica la presencia de  iii) the reaction is maintained until turbidity appears, becomes more viscous, pearly and / or acquires a grayish color, which indicates the presence of
nanoestructuras de plata; silver nanostructures;
iv) se diluye con un diluyente adecuado, se homogeneiza y centrifuga el producto de reacción  iv) is diluted with a suitable diluent, the reaction product is homogenized and centrifuged
obtenido, despreciando el sobrenadante, y las obtained, disregarding the supernatant, and
nanoestructuras sólidas recuperadas se lavan recovered solid nanostructures are washed
sucesivamente con el diluyente empleado y con etanol; successively with the diluent used and with ethanol;
v) finalmente, las nanoestructuras se suspenden en un disolvente adecuado para su conservación.  v) finally, the nanostructures are suspended in a suitable solvent for their conservation.
2. -Procedimiento para la obtención de 2. -Procedure to obtain
nanoestructuras de plata según la reivindicación 1, en el que la concentración de las disoluciones empleadas en los pasos del procedimiento son, 0,12-0,52 g de AgNO3 en 20 mi de etilenglicol; 0,15-0,45 g de PVP360 en 20 mi de etilenglicol; 0,0068-0,0300 g de CuCl2 en 10 mi de etilenglicol; 0,010-0,014 g de KBr en 10 mi de etilenglicol . Silver nanostructures according to claim 1, wherein the concentration of the solutions used in the steps of the process are 0.12-0.52 g of AgNO 3 in 20 ml of ethylene glycol; 0.15-0.45 g of PVP360 in 20 ml of ethylene glycol; 0.0068-0.0300 g of CuCl 2 in 10 ml of ethylene glycol; 0.010-0.014 g of KBr in 10 ml of ethylene glycol.
3. -Procedimiento para la obtención de 3. -Procedure to obtain
nanoestructuras de plata según la reivindicación 1, en el que en la etapa i) el etilenglicol calentado se mantiene a una temperatura de 160-180°C durante Silver nanostructures according to claim 1, wherein in step i) the heated ethylene glycol is maintained at a temperature of 160-180 ° C during
aproximadamente 30 minutos. approximately 30 minutes.
4. -Procedimiento para la obtención de 4. -Procedure to obtain
nanoestructuras de plata según las reivindicaciones 1 o 2, en el que en la etapa i) se añaden de 0,4 a 1,6 mi de la disolución de cloruro de cobre (II) . Silver nanostructures according to claims 1 or 2, wherein in step i) 0.4 to 1.6 ml of the copper (II) chloride solution are added.
5. -Procedimiento para la obtención de 5. -Procedure to obtain
nanoestructuras de plata según la reivindicación 1, en el que en la etapa ii), la bomba peristáltica opera a un caudal de 1,5 ml/min. Silver nanostructures according to claim 1, wherein in step ii), the peristaltic pump operates at a flow rate of 1.5 ml / min.
6. -Procedimiento para la obtención de 6. -Procedure to obtain
nanoestructuras de plata según la reivindicación 1, en el que en la etapa iii) el tiempo de reacción de silver nanostructures according to claim 1, wherein in step iii) the reaction time of
mantiene durante 15-90 minutos. Hold for 15-90 minutes.
7. -Procedimiento para la obtención de 7. -Procedure to obtain
nanoestructuras de plata según la reivindicación 1, en el que se utiliza acetona como diluyente en la etapa iv) . Silver nanostructures according to claim 1, wherein acetone is used as a diluent in step iv).
8. -Procedimiento para la obtención de 8. -Procedure to obtain
nanoestructuras de plata según la reivindicación 1 a 7, en el que, para la obtención esencialmente de nanohilos de plata, en la etapa ii) se adicionan 15 mi de la disolución de AgNO3 y 15 mi de la disolución de PVP360. The silver nanostructures according to claim 1 to 7, wherein, in order to obtain essentially silver nanowires, in step ii) 15 ml of the AgNO 3 solution and 15 ml of the PVP360 solution are added.
9. -Procedimiento para la obtención de nanoestructuras de plata según las reivindicaciones 1 a 7, en el que, para la obtención esencialmente de nanoestructuras cerradas o nanoanillos de plata, en la etapa ii) se adicionan 15 mi de la disolución de PVP360 y 15 mi de una mezcla formada con la disolución de AgNO3 y la disolución de KBr. 9. -Procedure to obtain Silver nanostructures according to claims 1 to 7, in which, in order to obtain essentially closed nanostructures or silver nano-rings, in step ii) 15 ml of the PVP360 solution and 15 ml of a mixture formed with the solution are added of AgNO 3 and the KBr solution.
10. -Nanohilos de plata obtenidos con el procedimiento según las reivindicaciones 1 a 8, 10. Silver nanowires obtained with the process according to claims 1 to 8,
caracterizados por que tienen un diámetro comprendido entre 100 y 300 nm y una longitud de 100 a 150 μm. characterized in that they have a diameter comprised between 100 and 300 nm and a length of 100 to 150 μm.
11. -Nanoanillos de plata obtenidos con el procedimiento según las reivindicaciones 1 a 7 y 9, caracterizados por que tienen un perímetro comprendido entre 30 y 100 mieras. 11. Silver nano-rings obtained with the process according to claims 1 to 7 and 9, characterized in that they have a perimeter comprised between 30 and 100 microns.
12. - Utilización de las nanoestructuras obtenidas mediante el procedimiento según cualquiera de las reivindicaciones 1 a 9, para su aplicación en revestimientos transparentes y conductores. 12. - Use of the nanostructures obtained by the method according to any of claims 1 to 9, for its application in transparent and conductive coatings.
13. -Utilización de los nanohilos de plata según la reivindicación 10, para su aplicación en 13. Use of the silver nanowires according to claim 10, for application in
revestimientos transparentes y conductores. transparent and conductive coatings.
14. -Utilización de los nanoanillos de plata según la reivindicación 11, para su aplicación en revestimientos transparentes y conductores. 14. Use of the silver nano-rings according to claim 11, for application in transparent and conductive coatings.
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