Photoconversion of light using metal supported atomic quantum clusters

Patent metadata

Field	Value
Publication number	US-10464047-B2
Application number	US-201214360658-A
Country	US
Kind code	B2
Filing date	Nov 30, 2012
Priority date	Dec 2, 2011
Publication date	Nov 5, 2019
Grant date	Nov 5, 2019

Abstract

The present invention discloses the use of a metal nanoparticle which comprises at least one semiconductor attached to it, wherein the at least one semiconductor is an atomic quantum cluster (AQC) consisting of between 2 and 55 zero-valent transition metal atoms, as photocatalysts in photocatalytic processes and applications thereof.

First claim

The invention claimed is:

1. A photocatalytic method directed to the reduction or oxidation of at least one organic or inorganic compound, or to water splitting, said method comprising
the step of contacting,
as photocatalyst, at least one metal nanoparticle having at least one of its dimensions between 1 nm and 60 mm comprising at least one semiconductor attached to it,
wherein the metal nanoparticles have shape of nanorods,
wherein the at least one semiconductor is an atomic quantum cluster (AQC) consisting of between 2 and 55 zero-valent transition metal atoms, wherein the zero-valent transition metal atoms of the AQCs are selected from Ag, Au, Pt, Pd, Co, Cu, Fe, Cr, Ni, Rh and combinations thereof, and
wherein the AQC and the metal nanoparticle have Fermi levels having a difference smaller than or equal to 1.5 eV at absolute zero,

with at least one electron acceptor molecule wherein its LUMO (lowest unoccupied molecular orbital) is lower than the Fermi level of the at least one metal nanoparticle comprising at least one AQC; wherein said one electron acceptor molecule is selected from acceptor dyes, oxygen (O 2 ), nitrates(NO 3 − ), hydrogen carbonates (HCO 3 − ), phosphates (PO 4 3− ), iron (III) compounds, manganese (IV) compounds, sulfates (SO 4 2− ), carbon dioxide, chloride ion (Cl − ) and chlorinated compounds, water, and alcohols; and
at least one electron donor molecule wherein its HOMO (highest occupied molecular orbital) is higher than the Fermi level of the at least one metal nanoparticle comprising at least one AQC; wherein said one electron donor molecule is selected from alcohols, water, compounds comprising S 2− , Se 2− ,SO 3 2− or SeO 3 2− ions, complexes such as EDTA, benzene, iodide salts, alkylammonium salts, alcohol amines, and organic acids;
by obtaining a composition comprising the metal nanoparticle, the at least one electron acceptor, and the at least one electron donor; and

(ii) irradiating said composition with a radiation in the ultraviolet to near infrared, provided that the nanoparticles have not been pre-irradiated, and
the step of irradiating the medium containing said at least one metal nanoparticle comprising at least one AQC, at least one electron acceptor and at least one electron donor with a radiation comprised in the ultraviolet to the near IR range which results in a chemical reaction involving the reduction of the electron acceptor and the oxidation of the electron donor.

2. The method according to claim 1 , wherein the zero-valent transition metal atoms of the AQCs are selected from Ag, Au, Pt, Pd and combinations thereof.

3. The method according to claim 1 wherein the metal of the metal nanoparticles is selected from Au, Ag, Co, Cu, Pt, Fe, Cr, Pd, Ni, Rh, Pb and combinations thereof.

4. The method according to claim 1 wherein the transition metal of the metal nanoparticles and the zero-valent transition metal atoms of the at least one atomic quantum cluster is the same.

5. The method according to claim 1 wherein the transition metal of the metal nanoparticles and the zero-valent transition metal atoms of the at least one atomic quantum cluster is different.

6. The method according to claim 1 wherein the atomic quantum cluster and the metal nanoparticles have Fermi levels at absolute zero, which its difference is not bigger than 1 eV.

7. The method according to claim 1 , wherein the organic or inorganic compound is a contaminant present in the air or in a solvent.

8. The method according to claim 1 , wherein the zero-valent transition metal atoms of the AQCs are Ag.

9. The method according to claim 1 , wherein the metal of the metal nanoparticles is selected from Ag, Au, Pt, Pd and combinations thereof.

10. The method according to claim 1 , wherein the metal of the metal nanoparticles is Au.

11. The method according to claim 1 , wherein the atomic quantum cluster and the metal nanoparticles have Fermi levels at absolute zero, which its difference is not bigger than 500 meV.

12. The method according to claim 1 , wherein the atomic quantum cluster and the metal nanoparticles have Fermi levels at absolute zero, which its difference is between 0 and 200 meV.

13. A photocatalyst composition comprising:
a metal nanoparticle having at least one of its dimensions between 1 nm and 60 mm comprising at least one semiconductor attached to it,
wherein the metal nanoparticles have shape of nanorods,
wherein the at least one semiconductor is an atomic quantum cluster (AQC) consisting of between 2 and 55 zero-valent transition metal atoms, wherein the zero-valent transition metal atoms of the AQCs are selected from Ag, Au, Pt, Pd, Co, Cu, Fe, Cr, Ni, Rh and combinations thereof, and
wherein the AQC and the metal nanoparticle have Fermi levels having a difference smaller than or equal to 1.5 eV at absolute zero,

at least one electron acceptor molecule wherein its LUMO (lowest unoccupied molecular orbital) is lower than the Fermi level of the metal nanoparticle comprising at least one AQC; wherein said one electron acceptor molecule is selected from acceptor dyes, oxygen (O 2 ), nitrates (NO 3 − ), hydrogen carbonates (HCO 3 − ), phosphates (PO 4 3− ), iron (III) compounds, manganese (IV) compounds, sulfates (SO 4 2− ), carbon dioxide, chloride ion (Cl − ) and chlorinated compounds, water, and alcohols; and
at least one electron donor molecule wherein its HOMO (highest occupied molecular orbital) is higher than the Fermi level of the metal nanoparticle comprising at least one AQC; wherein said one electron donor molecule is selected from alcohols, water, compounds comprising S 2− , Se 2− , SO 3 2− or SeO 3 2− ions, complexes such as EDTA, benzene, iodide salts, alkylammonium salts, alcohol amines, and organic acids.

14. The composition according to claim 13 in a medium selected from a liquid aqueous or non-aqueous medium, a gel, a polymer, an electrode or a surface medium, and wherein a plurality of said nanoparticles comprising atomic quantum clusters (AQC) is freely distributed in said medium.

15. A device for the photocatalysis of chemical reactions configured to comprise a medium containing
nanoparticles having at least one of its dimensions between 1 nm and 60 mm comprising at least one semiconductor attached to it,
wherein the metal nanoparticles have shape of nanorods,
wherein the at least one semiconductor is an atomic quantum cluster (AQC) consisting of between 2 and 55 zero-valent transition metal atoms, wherein the zero-valent transition metal atoms of the AQCs are selected from Ag, Au, Pt, Pd, Co, Cu, Fe, Cr, Ni, Rh and combinations thereof, and
wherein the AQC and the metal nanoparticle have Fermi levels having a difference smaller than or equal to 1.5 eV at absolute zero,

placed in contact with at least one charge carrier acceptor selected from a redox couple, an electrode or an electrode/redox couple.

16. A photovoltaic cell configured to comprise two electrodes with a self-assembled layer of nanoparticles, placed between the two electrodes in a disposition so that the different regions of each of the nanoparticles of the layer are in contact with the different electrodes,
said nanoparticles having at least one of its dimensions between 1 nm and 60 mm comprising at least one semiconductor attached to it,
wherein the metal nanoparticles have shape of nanorods,
wherein the at least one semiconductor is an atomic quantum cluster (AQC) consisting of between 2 and 55 zero-valent transition metal atoms, wherein the zero-valent transition metal atoms of the AQCs are selected from Ag, Au, Pt, Pd, Co, C

Assignees

• Univ Santiago Compostela

Inventors

• Lopez Quintela Manuel Arturo
• Rivas Rey Jose

Classifications

• C01B3/042

  Decomposition of water (by electrolysis of water C25B1/04) · CPC title

• B01J23/48

  Silver or gold · CPC title

• B01D2259/80

  Employing electric, magnetic, electromagnetic or wave energy, or particle radiation · CPC title

• B01D2255/802

  Photocatalytic · CPC title

• B01D2255/106

  Gold · CPC title