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    • 专利摘要:
    The present invention relates to the process for obtaining a nanocomposite consisting of clusters of one or several noble metals on a support of one or more nanomorphological metal oxides. The procedure consists of making a dispersion of nanoparticles of different metallic nature with precipitating agents, a hydrothermal synthesis and a reaction in agitation with compensated addition. Additionally, a spray and a heat treatment can be carried out to improve the properties and activity of the nanocomposite. The result of the object of the invention is a nanomorphological nanocomposite which includes dispersed metal clusters and which has a great interest for its great activity as a catalyst. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2589146A1
    申请号:ES201500357
    申请日:2015-05-08
    公开日:2016-11-10
    发明作者:María Elena FERNÁNDEZ GUTIÉRREZ；Laura GONZÁLEZ MIQUEO；José Luis MORACHO AMIGOT；Ángel MORACHO JIMÉNEZ；Ana BELÉN CUENCA
    申请人:Pavimentos De Tudela S A；Pavimentos De Tudela SA；
    IPC主号:
    专利说明:

    quot; NANOCOMPOSED OF NOBLE METAL CLUSTERS (V OTHER) ON NANOMORPHOLOGICAL METAL OXIDES. PREPARATION V USOSquot;
    DESCRIPTION OBJECT OF THE INVENTION
    The present invention relates to the process for obtaining a nanocomposite consisting of clusters of one or more noble metals on a support of one or more nanomorphological metal oxides.
    The process of obtaining consists of several stages, during which on the one hand a nanosoporte with nanorod structure is prepared, and on the other hand the deposition of metallic clusters of different nature is forced on said support. These stages include various operations that have to be carried out sequentially controlling the times, the degree of agitation and the temperature throughout the process.
    The nanocomposite produced from the process described in the present invention has shown great activity as a catalyst in oxidation reactions under aerobic conditions. It has been proven the high efficiency that it has as an oxidizing agent of various organic compounds, being able to oxidize substances such as volatile organic compounds (VOCs) present in the atmosphere of both indoor and outdoor environments, which are harmful to human health and environment. BACKGROUND OF THE INVENTION
    In recent years there has been an important development of nanotechnology, due to the large number of applications that have numerous elements and compounds of nanometric sizes (approximately 1-100 nm), which have a lot of properties of interest for various processes.
    Currently, the latest developments in nanotechnology are focusing on the development of metal clusters, seeking to increase the properties of these metals.
    Metal clusters are compounds whose particles are formed by a low number of atoms, in particular a number of atoms between 1 and 200 atoms and preferably between 1 O and 200 atoms, which have a particle size of less than 10 nm, preferably less than 1 nm. These compounds have a high specific surface area, becoming very reactive substances with high potential. This reactivity is directly related to different factors: the nature of the metal, the particle size, the morphology of the particles, their structure and dispersion, etc.
    Depending on the nature of the metal, the metal cluster may have different applications. In the specific case of gold and palladium dusters, they have an interesting utility in the field of catalysis. Gold and palladium dusters catalyze oxidation reactions in aerobic atmospheres. It has been proven that gold and palladium dusters catalyze oxidation reactions of Volatile Organic Compounds (VOCs), one of the main air pollutants in both indoor and outdoor environments, preferably alcohols, aldehydes and ketones.
    However, the main challenge is to find a balance between the efficiency of the metal cluster and their high cost. In spite of its high activity as a catalyst, it is very expensive compounds since its raw materials are noble metals and the complex synthesis process. Therefore, structures and particle morphologies that increase their activity should be sought, as well as synergies with other compounds present in the composition.
    There are several scientific articles, such as Jui-Ming Yeh et al. in the Joumal of Nanotechnology 2009, Kuyang Yiang et al. in Nanoletters 03.03.2003 vol. 3 and Leonor Alves et al. in the Joumal of the American Chemical Society 2011 vol. 133, which explain the deposition of gold dusters on a support of carbon nanotubes, doped and without doping, which possess catalytic activity in oxidation reactions. Along the same lines, patent with publication number EP 2402147 describes the process of manufacturing a gold nanocluster substrate on carbon nanotubes using an ultrasonic method by using polyelectrolytes.
    On the other hand, there is some work in which gold clusters have been deposited on an inorganic oxide, such as titanium oxide and cerium oxide. However, none of them use a cerium oxide with a special structure, as is the case of the cerium oxide with a nanorod structure used and described its method of production in the present invention. It has been observed that the synergy between the cluster of gold deposited in a dispersed manner, avoiding agglomerates, by means of a precipitating agent such as urea on cerium oxide synthesized with the characteristic structure of nanorods is crucial for the nanocomposite synthesized from the procedure described in the present invention. DESCRIPTION OF THE INVENTION
    The inventors have found a process for obtaining a nanocomposite consisting of dusters of one or more noble metals on a support of one or more nanomorphological metal oxides. By means of said process, a compound of great utility as a catalyst in oxidation reactions is obtained, being able to have a broad spectrum of applicability, being able to be used in numerous substrates and for a large number of processes. The present invention supposes a great advantage since a catalyst of a high activity is obtained, which is not inhibited in time, by a lower cost process than other existing alternatives.
    There is nothing in the state of the art that suggests a procedure for obtaining a nanocomposite based on metal clusters on a support of a nanomorphological inorganic oxide of a certain size and structure. Both the dispersion and size of the dusters and the structure and
    Inorganic oxide size obtained by the process of the invention are determinants for the activity and efficiency of the nanocomposite obtained.
    The process described in the invention is intended to synthesize a nanocomposite based on highly active metal clusters as a catalyst in oxidation reactions, being able to oxidize all types of organic compounds under normal atmospheric conditions, without the need for activation. The base of the high activity of the nanocomposite resides in the process of obtaining, from which a nanostructured support of a metal oxide with morphology of nanorods is synthesized, which has a synergy with the metallic clusters synthesized, dispersed and deposited according to the method of the invention Additionally, the procedure includes thermal and mechanical treatments that enhance the activity of the nanocomposite obtained from it.
    The process described in the present invention includes obtaining a nanocomposite that includes clusters of a noble metal on a nanomorphological support, characterized in that it comprises one or more of the following steps:
    • dispersion preparation of metal nanoparticles, mainly gold and / or palladium;
    • hydrothermal synthesis at controlled temperature and pressure;
    • reaction with intense agitation by compensated addition ~
    • solid / liquid separation process;
    • mechanical spraying and / or;
    • calcination. These stages include various operations that are to be taken to
    perform sequentially controlling the times, the degree of agitation and the temperature throughout the process.
    The noble metal clusters are compounds formed by a low number of metal atoms; specifically with a number of atoms included
    between 1-200 atoms, preferably between 10 and 200 atoms, with a size less than 10 nm, preferably less than 1 nm.
    As stated, the nanocomposite obtained by the process of the invention is a powerful catalyst in oxidation reactions, being able to degrade organic compounds without the presence of light being necessary. It has demonstrated the high efficiency it has in the degradation of important air pollutants such as Volatile Organic Compounds (VOCs), transforming them into carbon dioxide and water. Volatile organic compound is understood as a compound that contains carbon and one or more of the following elements: hydrogen, halogens, oxygen, sulfur, phosphorus, silicon or nitrogen. A volatile organic compound is any organic compound that has a vapor pressure of 0.01 kPa or more at 293.15 ° K, or that has equivalent volatility under the particular conditions of use. Their number exceeds a thousand, but the most abundant in the air are methane, tOluene, n-butane, i-pentane, ethane, benzene, npantane, propane, and ethylene, acetaldehyde, and formaldehyde.
    The process of the invention allows obtaining a nanocomposite that can be incorporated into any substrate without minimizing its activity, having a wide range of applications. In a very advantageous way it can be included in prefabricated concrete and / or cement derivatives, being able to be used in multiple applications in the construction of buildings, such as: enclosures, foundations, linear elements, forging elements, urban furniture, elements for civil works, pipes, paving, modular building or other specific solutions. The nanocomposite obtained can be used both indoors and outdoors with an important decontaminating effect. DESCRIPTION OF THE DRAWINGS
    To complement the description that is being made and in order to help a better understanding of the characteristics of the invention, according to a preferred example of practical implementation thereof, a set of drawings is attached as an integral part of said description. In an illustrative and non-limiting manner, the following has been represented:
    FIG. 1 shows an image of the structure, morphology and size of the preparation of CeOLNanorods object of the invention described in Example 1, obtained by means of a transmission electron microscope (TEM).
    FIG. 2 shows an image of the structure, morphology and size of a gold nanoc / uster deposited on a cerium oxide support object of the invention described in Example 2, obtained by means of a transmission electron microscope (TEM).
    FIG. 3 shows an image of the structure, morphology and size of a palladium nanocluster deposited on a nanomorphological titanium oxide support object of the invention described in Example 5, obtained by means of a transmission electron microscope (TEM).
    A PREFERRED EMBODIMENT OF THE INVENTION
    As mentioned above, the invention relates to a method of obtaining a nanocomposite that includes clusters of a noble metal on a nanomorphological support, characterized in that it comprises one or more of the following steps:
    • dispersion preparation of metal nano particles, mainly gold and / or palladium;
    • hydrothermal synthesis at controlled temperature and pressure;
    • reaction with intense stirring by compensated addition;
    • solid / liquid separation process;
    • mechanical spraying and / or;
    • calcination.
    The metal dusters can agglomerate in the composition thus losing part of their catalytic capacity, therefore in a preferred materialization the metal duster is deposited on a nano or sub-nanoparticulate support, thus decreasing the agglomeration of the dusters. Metallic clusters have a great and selective activity when they are deposited in a suitable support, where the dusters are immobilized. The metal-support interactions lead to an optimal dispersion of the metal clusters, the dusters stabilizing against agglomeration processes. The possible solid supports of the metal dusters according to the process of the invention are inorganic oxides, preferably cerium nanorods oxide and doped titanium oxide. The crystalline structure of these supports also plays a fundamental role in the activity and selectivity of the clusters themselves.
    More preferably, the process for obtaining noble metal clusters supported on inorganic oxide support includes a proportion of metal comprised between 0.001 and 5% of the total dry weight.
    The preferred support is cerium oxide with nanorod structure. Cerium oxide nanorods is obtained from a hydrothermal synthesis described in the invention and has a synergistic effect with the metal cluster under normal atmospheric conditions, enhancing its catalytic capacity. The presence of cerium oxide nanorocts favors the elimination and / or reduction of a large number of organic pollutants both indoors and outdoors, both in the presence and in the absence of light radiation.
    EXAMPLES Example 1: Preparation of Ce02 Nanorods
    In a Teflon reactor the Ce precursor (N03h'6H20 is added, and subsequently an aqueous NaOH solution is added to dissolve it. This mixture was stirred at room temperature for 10 min. Once the mixture is about 22-25 oC the reactor is closed well and is placed inside a drying oven for hydrothermal synthesis to take place, it is kept there without opening the stove at 100 ° C. for 24 hours, then it is removed from the stove and allowed to cool. cooled, it is filtered to recover the whitish precipitate that has formed and the precipitate is washed.Then, the recovered solid is transferred to a round bottom flask and dried using a vacuum adapter at 70-80 ° C during a night (4pm) Once the solid has been pre-dried, this powder is pulverized with the help of an agate mortar and is arranged in a series of ceramic pots for
    its calcination at 4000C for exactly 4 hours.
    Following this procedure, nanomorphological (nanorods) of stable cerium oxide (see F gets IG. one).hesupport
    Example 2: Nanomorphological deposition-precipitation of cerium oxide. fromaclusterfromgoldonsupport
    An aqueous solution A of tetrachloroauric acid hydrate (HAuCI4 x 3H20) was prepared. A mixture B of the cerium oxide_nanorods powder prepared was prepared
    according to example 1 of the present invention. Said mixture B was stirred at the speed of
    1200 rpm Subsequently, with the help of a 50-100 mL compensated pressure addition funnel, solution A was added over mixture B. Once all of solution A was added, an additional 16 mL of Millipore® water was poured onto the mixture that is now in the round bottom flask. Finally, 0.324 g (5.406 mmol) of urea was added in solid form. The synthesis was kept under stirring and at 80 ° C temperature for a total of 8 h. After these 8h, the stirring was interrupted and without stirring the flask contents were allowed to stand without transferring to any place for another 12h.
    After said period, it is filtered to recover the precipitate that has formed on standing and the precipitate is washed with deionized water. Subsequently, the recovered solid is transferred to a round bottom flask and the solid is dried using a vacuum adapter by applying vacuum at 80 ° C overnight (16h). Once the solid is pre-dried, this powder is sprayed with the help of an agate mortar and is arranged in a series of ceramic pots for calcination at 200 ° C for exactly 4 hours.
    Following this procedure, a solid nano morphological material is obtained containing a gold nanocluster deposited on a cerium oxide support (see FIG. 2) and whose percentage of metal determined by ICP is 0.717%.
    Example 3: Preparation of a mixed nanocomposite based on gold nanoclusters deposited on cerium oxide nanorods. diluted with nanomorphological titanium oxide.
    0.050 g of the nanomaterial prepared as described in example 2 of the present invention was taken and mixed with 0.63 g of nanomorphological titanium oxide (21 nm particle size, 35-65 m 2 / g (BET)) until achieving complete homogeneity with the help of an agate mortar.
    The samples thus prepared were kept protected from light and in the refrigerator until they were used.
    Example 4: Preparation of a mixed nanocomposite based on gold nanoclusters deposited on cerium oxide (IV) nanorods diluted with meso-structured silica.
    5 0.050 g of the nanomaterial prepared as described in Example 2 of the present invention was taken and mixed with 0.63 g of mesostructured silica (2.1-2.7 nm pore size, -1000 m 2¡g (BET »to achieve complete homogeneity with the help of an agate mortar.
    1 o The samples thus prepared were kept protected from light and in the refrigerator until they were used.
    Example 5: Nanomorphological preparation. fromananocluster ofpalladiumonoxidefromtitanium
    15 20 25 An aqueous solution A of Palladium nitrate (11) (Pd (N03) 2) and sodium nitrate (NaN03) was prepared. To prepare said solution A, 0.029 g (0.125 mmol) of the palladium precursor were weighed on the one hand and 0.034 g (0.4 mmol) of the sodium precursor on the other hand and dissolved in 100 mL of Millipore® water. In turn, 0.5 g (6.25 mmol) of nanomorphological titanium oxide (21 nm particle size, 35-65 m2 ¡g (BET) was added in a round bottom glass flask of 100 mL capacity ) similar to that used in example 3 of the present invention. The solution A, which has been previously prepared, is added little by little to this solid. The mixture-suspension thus formed was kept under stirring (1200 rpm) at room temperature (23-25 ° C) for 1 h. It must be protected from light by covering the flask with aluminum foil. After this time of co-impregnation, stirring was interrupted, excess excess water was removed by evaporation with the help of a rotary evaporator and heating at 60 ° C until a powder residue was obtained. The solid residue obtained after evaporation, which is found in the round bottom flask where the synthesis has been carried out, is further dried, with the
    help of an adapter, applying vacuum at 110 oC for 20h. Once pre-dried the
    solid, this powder is sprayed with the help of an agate mortar and is arranged in a series of ceramic pots for calcination at 400 ° C for exactly 2h.
    Following this procedure a nanomorphological solid material is obtained which contains a palladium nanocluster deposited on a titanium oxide support.
    (see FIG. 3) Ycuyo metal percentage determined by ICP is 1,733%.Example 6: Preparation of a mixed nanocomposite based on nanoclusters ofpalladium deposited on titanium oxide diluted in turn with titanium oxidenanomorphological
    0.025 g of the nanomaterial prepared as described in Example 5 of the present invention were taken and mixed with 0.63 g of nanomorphological titanium oxide (21 nm particle size, 35-65 m2 / g (BET »to achieve complete homogeneity with the help of an agate mortar.
    The samples thus prepared were kept protected from light and in a refrigerator until the time of use.
    权利要求:
    Claims (21)
    [1]
    1.-Procedure for obtaining a nanocomposite that includes
    noble metal clusters on a nanomorphological support, characterized in that it comprises one or more of the following stages:
    • dispersion preparation of metal nanoparticles;
    • hydrothermal synthesis;
    • reaction with intense stirring by compensated addition;
    • Solididollid separation process;
    • spray and / or;
    • calcination.
    [2]
    2. Method according to claim 1, characterized in that the solution of metal nanoparticles contains urea as a precipitating agent.
    [3]
    3. Method according to any of claims 1 to 2, characterized in that the hydrothermal synthesis occurs at a temperature between 50 and 200 OC.
    [4]
    4. Method according to any of claims 1 to 3, characterized in that the stirring reaction occurs at a temperature between 20 and 100 oC.
    [5]
    5. Method according to any of claims 1 to 4, characterized in that the liquid solid separation process can be carried out by centrifugation and / or filtration and / or vacuum filtration.
    [6]
    6. Method according to any of claims 1 to 5, characterized in that a vacuum drying process is carried out between 50 and 100 OC.
    [7]
    7. Method according to any of claims 1 to 5, characterized in that a drying process is carried out by an oven
    [8]
    8. Method according to any of claims 1 to 7, characterized in that the product is calcined at temperatures between 200 and 400 ° C.
    [9]
    9. Method according to any of claims 1 to 8, characterized in that the nanocomposite includes gold clusters.
    [10]
    10. Method according to claim 10, characterized in that the nanocomposite contains between 0.001 and 5% gold in its composition.
    [11]
    11. Method according to any of claims 1 to 8, characterized in that the nanocomposite includes palladium custers.
    [12]
    12. Method according to claim 11, characterized in that the nanocomposite contains between 0.001 and 5% palladium in its composition.
    [13]
    13. Method according to any of claims 1 to 12, characterized in that the nanocomposite contains a nanomorphological support formed by nanoparticles of an inorganic oxide.
    [14]
    14. Method according to any of claims 1 to 13, characterized in that the nanocomposite support is formed by cerium oxide.
    [15]
    15. Method according to claim 14, characterized in that the nanocomposite support is cerium oxide with nanorods structure.
    [16]
    16. Method according to any of claims 1 to 13, characterized in that the nanocomposite support is formed by titanium oxide.
    [17]
    17. Method according to any of claims 1 to 13, characterized in that the nanocomposite support is formed by doped titanium oxide.
    [18]
    18. Method according to any of claims 1 to 17, characterized in that the nanocomposite is dispersed in an inorganic oxide.
    [19]
    19. Method according to claim 18, characterized in that the inorganic oxide in which the nanocomposite is dispersed is nanostructured.
    [20]
    20.-Procedure according to any of claims 18 to 19,
    characterized in that the inorganic oxide in which the
    Nanocomposite is titanium oxide.
    [21]
    21. Method according to any of claims 18 to 20,
    5 characterized in that the inorganic oxide in which the nanocomposite is dispersed is doped titanium oxide. 22 .-- Nanocomposite characterized by having been synthesized according to any of claims 1 to 21.
    FIG. 1
    FIG. 2
    FIG. 3
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    同族专利:
    公开号 | 公开日
    ES2589146B1|2017-08-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2019088928A1|2017-11-02|2019-05-09|Nanyang Technological University|Bimetallic hybrid catalysts for catalytic oxidation of organic pollutants|
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