WO2010031890A1 - Synthèse de particules subnanométriques de au catalytiques portées sur des surfaces comportant des groupes amine - Google Patents

Synthèse de particules subnanométriques de au catalytiques portées sur des surfaces comportant des groupes amine Download PDF

Info

Publication number
WO2010031890A1
WO2010031890A1 PCT/ES2009/070389 ES2009070389W WO2010031890A1 WO 2010031890 A1 WO2010031890 A1 WO 2010031890A1 ES 2009070389 W ES2009070389 W ES 2009070389W WO 2010031890 A1 WO2010031890 A1 WO 2010031890A1
Authority
WO
WIPO (PCT)
Prior art keywords
particles
support structure
subnanometric
synthesis
amino groups
Prior art date
Application number
PCT/ES2009/070389
Other languages
English (en)
Spanish (es)
Inventor
Laura LECHUGA GÓMEZ
Ernesto MENDOZA GÓMEZ
Miguel Ángel CORREA DUARTE
Sobrido Marcos Sanles
Original Assignee
Consejo Superior De Investigaciones Científicas (Csic)
Universidad De Vigo
Fundació Privada Institut Catalá De Nanotecnología
LIZ MARZÁN, Luis
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Consejo Superior De Investigaciones Científicas (Csic), Universidad De Vigo, Fundació Privada Institut Catalá De Nanotecnología, LIZ MARZÁN, Luis filed Critical Consejo Superior De Investigaciones Científicas (Csic)
Publication of WO2010031890A1 publication Critical patent/WO2010031890A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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 relates to structures composed of Au particles of subnanometric size ( ⁇ 3 nm) synthesized on a surface coated with (molecules or) polymers having amino groups. Said invention also refers to its method of obtaining and its use as catalysts for the industry.
  • the present invention provides a system composed of Au subnanometric particles anchored on surfaces with amino groups, in addition to their synthesis and their application in catalytic processes.
  • the synthesis method proposed in the invention achieves the scaling of the production of Au sub-nanometer particles with the active surface for efficient catalysis.
  • the Au particles of the present invention with a sub-nanometer size have exceptional catalytic properties that may be of special interest to the chemical and pharmaceutical industries, among others. In this way, new catalytic strategies may arise as a result of the unique catalytic properties contributed by these Au sub-nanometer structures.
  • the invention described herein proposes the manufacture of subanometric particles of Au synthesized and anchored on structures that act as support, for example carbon nanotubes, with the advantage of industrial scaling thereof and having said catalysts an active surface that increases its effectiveness .
  • Support structures coated and stabilized with polymers containing amino groups are presented as a means for obtaining and stabilizing these sub-nanometer gold particles.
  • These polymers, such as polyallylamine hydrochloride cover the surface of the support and the amino groups present act as nucleation centers where the sub-nanometer particles of Au are to be reduced, stabilized and anchored.
  • the present invention relates to the obtaining and stabilization of subanometric particles of Au by means of a reduction induced by the amino groups present in the polymer that covers the support structure. Therefore, by means of this synthetic method, the aggregation and agglomeration of sub-nanometer particles is prevented, which would cause the loss of their properties, while allowing the scaling of their production indispensable for its industrial application.
  • a first aspect of the present invention refers to a process for obtaining a composition of Au subnanometric particles anchored on a support structure comprising the following steps: a. coating the support structure with a polymer or other compound containing amino groups; and b. add, to the coated support structure obtained in (a), gold cations (Au +3 or Au + ) in the presence of a reducing agent, such as, but not limited to sodium citrate, and in aqueous solution.
  • a reducing agent such as, but not limited to sodium citrate
  • subnanometric particles is understood in the present invention to particles that are up to 3 nm in diameter and preferably up to 1 nm in diameter.
  • support structure is understood in the present invention the material on which the sub-nanometer particles are grown after being coated with polymer containing amino groups, such as, but not limited to carbon nanotubes or polystyrene balls.
  • polymer containing amino groups means in the present invention any polymer with amino groups in its chemical structure.
  • examples of this type of polymers could be, but not limited to polyallylamine hydrochloride or polyaniline.
  • This polymer also acts as a reducing agent for Au cations with the help of sodium citrate. It is important to note that sub-nanometer nanoparticles are only formed in the presence of the reducing agent, such as sodium citrate, which is generally used as a stabilizer and weak reducer.
  • the reducing agent such as sodium citrate
  • polymers that do not contain amino groups such as sodium polystyrene sulfonate, do not give rise to subnanometric particles even in the presence of sodium citrate, highlighting the importance of the polymer's amino groups.
  • a second aspect of the present invention relates to a composition of subanometric particles of Au synthesized and anchored on a support structure whose surface is covered by a polymer containing amino groups obtainable by the process of the invention.
  • a third aspect of the present invention refers to the use of the composition of Au subnanometric particles anchored on the support structures as catalysts, preferably as a chemical catalyst.
  • Fig. 1.A.- It shows the transmission electron microscopy image of the sub-nanometer particles of Au in the carbon nanotube wall.
  • Fig. 1.B.- It shows the high resolution electron microscopy image, in detail, of the sub-nanometer particles of Au in the carbon nanotube wall.
  • Fig. 1.C.- Shows the transmission electron microscopy image of a polystyrene sphere used as support for the synthesis.
  • Fig. 1.D.- It shows the transmission electron microscopy image of the edge of the polystyrene sphere where the presence of Au sub-nanometer particles can be seen.
  • Fig. 1.E.- Represents a scheme of the synthesis procedure.
  • Fig. 1.F.- Arrhenius graph for the reaction of reduction of potassium hexacyanoferrate (III) by means of sodium borohydride.
  • the lower curve shows the data for 15 nm particles and the upper curve for the subanometric particles of Au anchored in the wall of carbon nanotubes.
  • Carbon nanotubes were suspended in ultrapure water (18 M ⁇ cm) following the protocol of M. A. Correa-Duarte, N. Sobal, L. M. Liz-Marzán, M. Giersig, Adv. Mater. 2004, 16, 2179.
  • the carbon nanotubes were suspended in an aqueous solution of 1% by weight of polyallylamine hydrochloride to a concentration of 150 mg / L.
  • the suspension was dispersed with the help of an ultrasonic snorer to ensure good homogeneity and ensure that the carbon nanotubes were suspended individually.
  • the excess polyallylamine hydrochloride was removed by several cycles of centrifugation and redispersion until a concentration of 0.1 mg / mL of carbon nanotubes was achieved.
  • FIG. 1A shows an image of transmission electron microscopy of the sub-nanometer particles of Au in the carbon nanotube wall. A higher resolution image of the compound can be seen in Figure 1 B, where the atomic carbon layers that form the nanotube and a large number of homogeneous subnanometric particles attached to the nanotube wall can be seen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne des structures composées de particules de Au de taille subnanométrique (<3 nm) synthétisées sur une surface recouverte de molécules ou de polymères qui comportent des groupes amine. L'invention concerne également un procédé permettant de produire ces structures, ainsi que leur utilisation comme catalyseurs pour l'industrie.
PCT/ES2009/070389 2008-09-22 2009-09-18 Synthèse de particules subnanométriques de au catalytiques portées sur des surfaces comportant des groupes amine WO2010031890A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200802676A ES2335467B1 (es) 2008-09-22 2008-09-22 Sintesis de particulas subnanometricas de au cataliticas soportadas en superficies con grupos amino.
ESP200802676 2008-09-22

Publications (1)

Publication Number Publication Date
WO2010031890A1 true WO2010031890A1 (fr) 2010-03-25

Family

ID=41818474

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/ES2009/070389 WO2010031890A1 (fr) 2008-09-22 2009-09-18 Synthèse de particules subnanométriques de au catalytiques portées sur des surfaces comportant des groupes amine

Country Status (2)

Country Link
ES (1) ES2335467B1 (fr)
WO (1) WO2010031890A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102218542A (zh) * 2011-05-12 2011-10-19 陕西科技大学 一种纳米金的制备方法
CN103418800A (zh) * 2013-07-19 2013-12-04 长沙铂鲨环保设备有限公司 一种纳米金的制备方法
EP2792410A1 (fr) 2013-04-15 2014-10-22 Goldemar Solutions, S.L. Procédé de préparation d'un catalyseur comprenant des nanoparticules d'or, le catalyseur et son utilisation
CN109128216A (zh) * 2018-10-26 2019-01-04 启东科赛尔纳米科技有限公司 常温下金纳米粒子的合成方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008078970A1 (fr) * 2006-12-27 2008-07-03 Daegu Gyeongbuk Institute Of Science & Technology Préparation in situ de substrats présentant des nanoparticules d'or dispersées

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008078970A1 (fr) * 2006-12-27 2008-07-03 Daegu Gyeongbuk Institute Of Science & Technology Préparation in situ de substrats présentant des nanoparticules d'or dispersées

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DANIEL, M.C. ET AL.: "Gold nanoparticles: assembly, supramolecular chemistry, quantum-size- related properties, and applications toward biology, catalysis, and nanotechnology.", CHEMICAL REVIEWS, vol. 104, 2004, pages 293 - 346 *
JIANG, L. ET AL.: "Modified carbon nanotubes: an effective way to selective attachment of gold nanoparticles.", CARBON, vol. 41, 2003, pages 2923 - 2929 *
JIANG, L. ET AL.: "Selective attachment of gold nanoparticles to nitrogen-doped carbon nanotubes.", NANO LETTERS, vol. 3, no. 3, 2003, pages 275 - 277 *
SANTHOSH, P. ET AL.: "Gold nanoparticles dispersed polyaniline grafted multiwall carbon nanotubes as newer electrocatalysts: Preparation and performances for methanol oxidation.", JOURNAL OF CATALYSIS, vol. 238, 2006, pages 177 - 185 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102218542A (zh) * 2011-05-12 2011-10-19 陕西科技大学 一种纳米金的制备方法
EP2792410A1 (fr) 2013-04-15 2014-10-22 Goldemar Solutions, S.L. Procédé de préparation d'un catalyseur comprenant des nanoparticules d'or, le catalyseur et son utilisation
CN103418800A (zh) * 2013-07-19 2013-12-04 长沙铂鲨环保设备有限公司 一种纳米金的制备方法
CN109128216A (zh) * 2018-10-26 2019-01-04 启东科赛尔纳米科技有限公司 常温下金纳米粒子的合成方法

Also Published As

Publication number Publication date
ES2335467A1 (es) 2010-03-26
ES2335467B1 (es) 2010-12-30

Similar Documents

Publication Publication Date Title
Sasmal et al. Landscaping covalent organic framework nanomorphologies
Negri et al. Carbon nanotubes in biomedicine
Chen et al. Methods and mechanism for improvement of photocatalytic activity and stability of Ag3PO4: a review
Ariga et al. Challenges and breakthroughs in recent research on self-assembly
US7829119B2 (en) Method to fabricate microcapsules from polymers and charged nanoparticles
Wang et al. Emerging materials for the fabrication of micro/nanomotors
ES2247680T3 (es) Metal poroso y metodo para lograr su preparacion.
Hu et al. Fabrication and application of inorganic hollow spheres
Xie et al. Nanosheet-based titania microspheres with hollow core-shell structure encapsulating horseradish peroxidase for a mediator-free biosensor
Yan et al. Biocompatible, hydrophilic, supramolecular carbon nanoparticles for cell delivery
Kalantari et al. Highly thiolated dendritic mesoporous silica nanoparticles with high-content gold as nanozymes: the nano-gold size matters
ES2335467B1 (es) Sintesis de particulas subnanometricas de au cataliticas soportadas en superficies con grupos amino.
Singh et al. Carbon Nanotube and Gold‐Based Materials: A Symbiosis
Han et al. A new model for the synthesis of hollow particles via the bubble templating method
WO2013057349A1 (fr) Procédé pour obtenir un substrat avec des nanoagrégats d&#39;au fixés sur sa surface, et substrat et catalyseur obtenus selon ledit procédé
Liu et al. Sub-angstrom gold nanoparticle/liposome interfaces controlled by halides
Nordlund et al. A membrane-reconstituted multisubunit functional proton pump on mesoporous silica particles
Cai et al. Hemoglobin‐CdTe‐CaCO3@ Polyelectrolytes 3D Architecture: Fabrication, Characterization, and Application in Biosensing
Polat et al. Effect of surface–molecule interactions on molecular loading capacity of nanoporous gold thin films
Liu et al. Fabrication of nanohybrids assisted by protein-based materials for catalytic applications
Ariga et al. Recent progresses in bio-inorganic nanohybrids
Generalova et al. One-dimensional necklace-like assemblies of inorganic nanoparticles: Recent advances in design, preparation and applications
Liu et al. Peptoid-based hierarchically-structured biomimetic nanomaterials: Synthesis, characterization and applications
Wang et al. Nanoparticles change the ordering pattern of n-carboxylic acids into nanorods on HOPG
Gao et al. Defect-induced double-stranded DNA unwinding on graphene

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09814134

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09814134

Country of ref document: EP

Kind code of ref document: A1