Photocatalytic generation of singlet oxygen for air purification

Patent metadata

Field	Value
Publication number	US-2022211894-A1
Application number	US-202117524654-A
Country	US
Kind code	A1
Filing date	Nov 11, 2021
Priority date	Nov 12, 2020
Publication date	Jul 7, 2022
Grant date	—

Abstract

Aspects disclosed herein include a system for generating singlet oxygen in a gas, the system comprising: a substrate; and hexanuclear clusters operably immobilized on at least a portion of the substrate; wherein each hexanuclear cluster comprises a photosensitive octahedral core complex characterized by formula FX1a: M6X8 (FX1a); wherein each M is independently Mo, W, or Re; wherein each X is independently a halide anion ligand; wherein the clusters are exposed to the gas and the gas comprises O2 gas; wherein the clusters are exposed to a light; and wherein each hexanuclear cluster is a photosensitizer configured to generate the gaseous singlet oxygen when irradiated by the light in the presence of the O2 gas.

First claim

1 . A system for generating singlet oxygen in a gas, the system comprising:
a substrate; and hexanuclear clusters operably immobilized on at least a portion of the substrate;
wherein each hexanuclear cluster comprises a photosensitive octahedral core complex characterized by formula FX1a:
M 6 X 8   (FX1a);

wherein each M is independently Mo, W, or Re;
wherein each X is independently a halide anion ligand;
wherein the clusters are exposed to the gas and the gas comprises at least O 2 gas; wherein the clusters are exposed to a light; and wherein each hexanuclear cluster is a photosensitizer configured to generate the gaseous singlet oxygen when irradiated by the light in the presence of the O 2 gas.

2 . A system for inactivation of pathogens via singlet oxygen, the system comprising:
a photosensitizing component for generating gaseous singlet oxygen, comprising:
a substrate; and
hexanuclear clusters operably immobilized on the substrate;
wherein each hexanuclear cluster comprises a photosensitive octahedral core complex characterized by formula FX1a:
M 6 X 8   (FX1a);

wherein each M is independently Mo, W, or Re; and
wherein each X is independently a halide anion;
a conveyed gas in gas-communication with the photosensitizing component;
wherein the clusters are exposed to the gas and the gas comprises at least O 2 gas;
a light source configured to emit a light onto the hexanuclear clusters, the light being capable of photoactivating the hexanuclear clusters; wherein each hexanuclear cluster is a photosensitizer configured to generate the gaseous singlet oxygen when irradiated by the light in the presence of the O 2 gas.

3 . The system of claim 2 being a system for inactivation of airborne pathogens or a system for inactivation of pathogens on a surface, wherein:
the conveyed gas comprises the airborne pathogens to inactivate the airborne pathogens in the gas via the gaseous singlet oxygen; or
the conveyed gas, having the generated gaseous singlet oxygen, flows from the photosensitizing component onto the surface and the conveyed gas comprises the generated gaseous singlet oxygen at the surface.

4 . (canceled)

5 . The system of claim 1 , wherein the core complex is characterized by formula FX1b or FX1c:
Mo 6 X 8   (FX1b); or
Mo 6 Cl 8   (FX1c).

6 . The system of claim 1 , wherein each hexanuclear cluster is independently neutral, cationic, or anionic; wherein each cationic cluster, if present, is charge-balanced with one or more counterions; and wherein each anionic cluster, if present, is charge-balanced with one or more counterions.

7 . The system of claim 1 , wherein each of the hexanuclear clusters is independently characterized by formula FX2a, FX2b, or FX2c:
M 6 X 8 L 6   (FX2a);
M 6 X 8 L 4   (FX2b); or
M 6 X 8 L 2   (FX2c); wherein:
each M is independently Mo or W; each X is independently a halide anion ligand; and each L is independently an organic or inorganic monoanion ligand.

8 . The system of claim 7 , wherein each L is independently Cl, Br, I, C, or O.

9 . The system of claim 1 , wherein each of the hexanuclear clusters is independently characterized by formula FX2d, FX2e, or FX2f:
M 6 X 8 (L′) 6[[+]]− −  (FX2d);
M 6 X 8 (L′) [[+]]− −  (FX2e); or
M 6 X 8 (L′) 2[[+]]− −  (FX2f); wherein:
each M is independently Mo or W; each X is independently a halide anion ligand; and each L′ is independently one or more organic or inorganic monoanion and/or polyanion ligands.

10 . The system of claim 1 , wherein each of at least a fraction of the hexanuclear clusters is independently a compound characterized by formula FX2a, FX2b, or FX2c:
(M 6 X 8 L 6 ) 2− (A C ) p 2+   (FX3a);
(M 6 X 8 L 4 )(A N ) n   (FX3b); or
(M 6 X 8 L 2 ) 2+ (A A ) m 2−   (FX3c); wherein:
each M is independently Mo or W; each X is independently a halide anion ligand; each L is independently an organic or inorganic monoanion; p is 2 and each A C is independently a counterion being an organic or inorganic monocation or p is 1 and A C is a counterion being an organic or inorganic dication; m is 2 and each A A is independently a counterion being an organic or inorganic monoanion or m is 1 and A A is a counterion being an organic or inorganic dianion; and n is an integer selected from the range of 1 to 2 and AN is an organic or inorganic neutral Lewis base ligand.

11 . The system of claim 10 , wherein each A N is independently selected from the group consisting of N, a substituted or unsubstituted pyridine, a substituted or unsubstituted amine, a substituted or unsubstituted methide, carbon monoxide, a substituted or unsubstituted triphenylphosphine, a substituted or unsubstituted triphenylarsine, a substituted or unsubstituted dimethylsulfide, a substituted or unsubstituted diemthylselenide, ammonia, and any combination thereof; and wherein each A C is independently selected from the group consisting of a metal monocation, NH 4+ , tetrabutylammonium, tetramethylammonium, tetraethylammonium and any combination thereof.

12 . (canceled)

13 . The system of claim 1 , wherein each of the hexanuclear clusters comprises a composition characterized by formula FX4:
M 6 X 12   (FX4); wherein:
each M is independently Mo or W; and each X is independently a halide anion.

14 . (canceled)

15 . The system of claim 1 , wherein each M is Mo or W and each X is Cl, Br, or I.

16 . (canceled)

17 . The system of claim 1 , wherein the substrate has a composition characterized as a metal oxide, nonmetal oxide, a polymer, a coordination polymer or polymeric material, an organofluoride material, an allotrope of carbon, or a combination of these.

18 . The system of claim 1 , wherein the substrate comprises a plurality of carbon-fluoride bonds.

19 . (canceled)

20 . The system of claim 1 , wherein the portion of the substrate having the clusters operably immobilized thereon has a porosity sufficient to be permeable by O 2 gas.

21 . (canceled)

22 . The system of claim 1 , wherein the substrate comprises metal oxide or non-metal oxide particles having the clusters operably connected or associated thereto.

23 . The system of claim 1 , wherein at least a fraction of the hexanuclear clusters are non-covalently attached to the substrate.

24 . The system of claim 1 , wherein at least a fraction of the hexanuclear clusters are covalently attached to the substrate.

25 . The system of claim 24 , wherein at least a fraction of the hexanuclear clusters are covalently attached to a portion of the substrate having a metal oxide or nonmetal oxide composition via a silane compound or silane group.

26 . (canceled)

27 . The system of claim 1 , wherein at least a fraction of the hexanuclear clusters are covalently attached to the substrate accordingly to formula FX10a, FX10b, FX10c, FX10d, FX10e, or FX10f:
[S mo,nmo ]-Z 1 -Z 2 -[(M 6 X 8 L 6 ]  (FX10a);
[S mo,nmo ]-Z 1 -Z 3 -[(M 6 X 8 L 4 ]  (FX10b);
[S mo,nmo ]-Z 1 -Z 4 -[(M 6 X 8 L 2 ]  (FX10c);
[S pol ]-Z 5 -[(M 6 X 8 L 6 ]  (FX10d);
[S pol ]-Z 6 -[(M 6 X 8 L 4 ]  (FX19e); or
[S pol ]-Z 7 -[(M 6 X 8 L 2 ]  (FX10f); wherein:
S mo,nmo is a portion of the substrate having a composition characterized as a metal oxide or a non-metal oxide; S pol is a portion of the substrate that is a polymer; Z 1 is a

Assignees

• California Inst Of Techn

Inventors

• Grubbs Robert H
• Blumenfeld Carl M
• Gray Harry B
• Rossman George R

Classifications

• C01G39/04

  Halides · CPC title

• C01G41/04

  Halides · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• C01B13/02

  Preparation of oxygen (by liquefying F25J) · CPC title