Procedure for obtaining a substrate with Au nanoclusters attached to its surface, and the substrate and catalyst obtained through this procedure

Abstract

Method for producing a substrate with Au (gold) nanoclusters affixed to the surface thereof and substrate and catalyst obtained by means of said method. The method consists in preparing a solution containing, in disperse form, Au nanoclusters and, also in disperse form, a substrate with a surface functionalized with a polyelectrolyte that confers a net electric charge thereon, and in intensely agitating said solution to affix Au nanoclusters to the substrate surface. This results in a substrate that has a surface with Au nanoclusters affixed in disperse form, significantly without clusters. The invention also relates to a catalyst that comprises said substrate with Au nanoclusters affixed to the surface thereof. Said catalyst is particularly suitable for use in oxidation reactions.

Claims

1. A procedure for obtaining a substrate with Au nanoclusters attached to its surface, characterised in that it involves: preparing a solution with dispersed Au nanoclusters as well as a dispersed form of a substrate whose surface is functionalised with a polyelectrolyte which gives it a net electrical charge; and subjecting said solution to agitation in order to cause Au nanoclusters to attach to the surface of the substrate; wherein the substrate comprises inorganic oxide nanoparticles, and wherein the inorganic oxide comprises Fe.sub.2O.sub.3.

2. The procedure according to claim 1, characterised in that the agitation of the solution intended to cause Au nanoclusters to attach to the surface of the substrate is performed by subjecting the solution to ultrasonication.

3. The procedure according to claim 1, characterised in that it includes a prior stage of Au nanocluster formation carried out by subjecting a solution comprising at least one precursor of Au and a polyelectrolyte to ultrasonication.

4. The procedure according to claim 1, wherein said solution, which is subjected to agitation to provoke the Au nanoclusters to attach to the substrate surface, contains a weight in Au nanoclusters of between 0.1% and 10% with respect to the weight of the substrate.

5. The procedure according to claim 1, characterised in that, after the solution has been subjected to agitation in order to cause the Au nanoclusters to attach to the substrate surface, a treatment is applied to separate the solution from the substrate with Au nanoclusters attached to its surface either through drying, filtration or lyophilising of the solution, with the resulting substrate being comprised of loose powder.

6. The procedure according to claim 1, characterised in that, after the solution has been subjected to agitation in order to cause the Au nanoclusters to attach to the substrate surface, a treatment is applied to separate the solution from the substrate with Au nanoclusters attached to its surface through the application of a suspension containing the substrate to the support material surface, where the final result is a support material with the substrate attached to its surface.

7. The procedure according to claim 1, characterised in that the action of subjecting the solution to agitation in order to cause Au nanoclusters to attach to the substrate surface is accompanied, simultaneously or sequentially, by a thermal treatment in which the temperature rises to between 200° C. and 400° C.

8. The procedure of claim 1 wherein: the procedure has a prior stage of Au nanocluster formation carried out by subjecting a precursor solution comprising at least one precursor of Au and a polyelectrolyte to ultrasonication; the agitation of the solution intended to cause Au nanoclusters to attach to the surface of the substrate is performed by subjecting the solution to ultrasonication; the substrate comprises one or more of the nanostructured materials; the solution which is subjected to agitation to provoke the Au nanoclusters to attach to the substrate surface contains a weight in Au nanoclusters of between 0.1% and 10% with respect to the weight of the substrate; the subjecting the solution to agitation in order to cause Au nanoclusters to attach to the substrate surface is accompanied, simultaneously or sequentially, by a thermal treatment in which the temperature rises to between 200° C. and 400° C.

9. The procedure of claim 1 wherein the inorganic oxide consisting of Fe.sub.2O.sub.3.

10. The procedure of claim 1 wherein the inorganic oxide comprises CeO.sub.2.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an atomic force microscopy image showing Au nanoclusters obtained during a previous stage of the process according to the invention, wherein the nanoclusters are formed from Au through the ultrasonication of an aqueous solution whose solutes are an Au precursor and a polyelectrolyte.

(2) FIG. 2 is an image of a transmission electron microscope showing a detailed area of the powder product obtained as the end result of the procedure according to the invention, wherein the Au nanoclusters are supported on the carbon nanotube surface.

EXAMPLES OF EMBODIMENTS

Example 1

(3) The following describes in a non-limitative way an example of the embodiment of the invention.

(4) The formation of Au nanoclusters occurs at an earlier stage consisting of ultrasonication (submitting to ultrasound) of an aqueous solution whose solutes are a precursor to Au and a polyelectrolyte. The Au precursor is tetrachloroauric acid (HAuCl.sub.4) and the polyelectrolyte precursor is the sodium salt from polymethacrylic acid (PMAA). The resulting solution has a final gold concentration of 0.02 mg/ml. The molar ratio between gold and the PMAA carboxylate groups is 2. The pH of the solution is adjusted to 4.5 by the addition of nitric acid (HNO.sub.3), and the oxygen dissolved in the solution was eliminated by bubbling argon gas for 30 minutes. After the oxygen is removed from the solution, it is ultrasonicated for about 20 minutes with a Branson 250D probe sonicator operated at 200 W to form Au nanoclusters. The volume of the solution is 100 ml.

(5) As a result of this previous stage, an aqueous solution of Au nanoclusters with a concentration of 0.02 mg of Au nanoclusters per ml of aqueous solution is obtained.

(6) FIG. 1 shows an atomic force microscopy image of the Au nanoclusters obtained, having been placed on a mica surface in order to capture the image. Numerous gold nanoclusters are clearly visible on the mica surface.

(7) A solution is then prepared which contains the dispersed Au nanoclusters formed in the previous step and a dispersed substrate whose surface is functionalised with a polyelectrolyte which gives it a net electric charge. In this example of embodiment, the substrate is comprised of carbon nanotubes, and the polyelectrolyte used to functionalise the surface of the substrate is polyallylamine.

(8) The functionalised carbon nanotubes with polyallylamine are prepared using the following protocol. A suspension of carbon nanotubes is prepared in a 1% aqueous solution of polyallylamine hydrochloride to achieve a concentration of 1 mg of carbon nanotubes per ml of aqueous solution. The suspension is dispersed using an ultrasonic Branson 250D probe sonicator operated at 250 W for 30 minutes to ensure that the carbon nanotubes are suspended individually. The volume of the solution is 100 ml.

(9) This aqueous solution of carbon nanotubes is mixed with the aqueous solution of Au nanoclusters obtained in the previous step, in a proportion wherein the weight ratio between the Au nanoclusters and the carbon nanotubes is 1% in Au with respect to carbon nanotubes.

(10) While this mixture, comprising the solution of Au nanoclusters in dispersed form and the carbon nanotube substrate whose surface is functionalised with a polyelectrolyte which gives it a net electrical charge is prepared, ultrasonication of the solution is performed for 15 minutes with a 250D probe sonicator operated at 100 W. The ultrasonication causes dispersion of the Au nanoclusters on the surface of carbon nanotubes, facilitating the attachment of Au nanoclusters to the surface without forming agglomerates due to the polyelectrolyte that gives it a net electrical charge. This process yields a final aqueous solution of carbon nanotubes with Au nanoclusters attached to its surface.

(11) Finally, a separation stage is implemented to separate the carbon nanotubes with Au nanoclusters attached to their surface from this final solution. The separation is achieved through filtration using a vacuum filter. Alternatively, the separation can be carried out through drying or lyophilisation with equivalent results: a powder consisting of carbon nanotubes with fixed Au nanoclusters on its surface.

(12) Optionally, to increase the efficiency of the process for attaching the Au nanoclusters to the substrate surface (metal-substrate interaction process) ultrasonication of the solution should be simultaneously or sequentially accompanied by a thermal treatment in which the temperature of the substrate with Au nanoclusters anchored to its surface rises to between 200° C. and 400° C.

(13) FIG. 2 is a transmission electron microscopy image showing a detailed area of the powder obtained. As shown, the Au nanoclusters are attached to the surface of the carbon nanotubes. The nanoclusters are visible as dark spots on the graphitic structure of the carbon nanotubes. It should be noted that the number of nanoclusters in the image is not large as they are deposited in a small proportion, which in this example is 1% by weight.

Example 2

(14) Following the same procedure than Example 1 described above, with the only difference that the final stage, the separation of the carbon nanotubes with the

(15) attached Au nanoclusters on the surface from the solution, is made of differently.

(16) Starting from the already described final solution obtained with the synthesis process or preparing from this solution another solution or suspension of carbon nanotubes with Au nanoclusters in a solvent such as water, ethanol or any other compatible solvent at a concentration typically 0.5 mg/ml. This solution or slurry is impregnated into the surface of a support material preferably porous, which in this example is formed of a porous ceramic monolith, as an example one of those used in automobile catalytic converters. The final support material is obtained after performing a drying operation to evaporate the solvent, performed for example in an oven at a temperature typically of 60° C. In this case, the material is formed by the porous ceramic monolith with the carbon nanotubes with Au nanoclusters attached on its surface. Thus, the final product is not a carbon nanotube powder with Au nanocluster as in Example 1, but a porous support material to the surface of which are fixed the carbon nanotubes with Au nanoclusters. These carbon nanotubes are equivalent to those shown in FIG. 2 discussed in Example 1, with the only difference that, instead of being in powder form, are fixed to the support material consisting of a porous ceramic monolith. Both the product obtained in Example 1 and Example 2 are advantageously applicable as catalysts in oxidation reactions. The choice between any of them depends on whether a catalyst is required in powder form, as in Example 1, or a fixed on a catalyst support material as in Example 2.