# US 10,118,155 B2 · Method of metallic clusters fabrication with desired size using scanning tunneling microscopy tip induced reactions

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- Number: US 10,118,155 B2
- Document ID: US10118155B2
- Status: Granted
- Kind: B2
- Application number: 15/511,469
- Filed: 2016-08-11
- Published: 2017-10-05
- Granted: 2018-11-06
- Earliest claimed: 2015-08-14
- Assignees: Sabic Global Technologies B.V.; UCL Business PLC
- Applicants: SABIC Global Technologies B.V.; UCL Business PLC
- Inventors: Andy Mellor; Chi Yim; Chi Pang; Geoff Thornton; Hicham Idriss
- Web page: https://patentgrep.com/patent/US10118155B2

## CPC

- B01J 23/52: Gold
- B01J 21/063: {Titanium; Oxides or hydroxides thereof}
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 35/39: Photocatalytic properties
- B01J 35/396: {Distribution of the active metal ingredient}
- B01J 37/342: {of electric, magnetic or electromagnetic fields, e.g. for magnetic separation}
- B82B 3/0004: {Apparatus specially adapted for the manufacture or treatment of nanostructural devices or systems or methods for manufacturing the same}
- C23C 14/18: on other inorganic substrates
- C23C 14/58: After-treatment
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B82B: NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

A method of transferring a single metal atom from a first location to a second location on the surface of a metal oxide is disclosed. The method includes obtaining a material having a first metal atom deposited on a first oxygen atom vacancy of the metal oxide and transferring the first metal atom of the metal on the first oxygen atom vacancy to a second location on the metal oxide by applying a voltage to the first metal atom. The second location can be a second metal atom on a second oxygen atom vacancy of the metal oxide, where the first and second metal atoms form a first metal atom-second metal atom species, or a metal atom of the metal oxide, where the first metal atom and the metal atom of the metal oxide forms a first metal atom-metal atom of the metal oxide species.

## Claims

### Claim 1

A method of transferring a single metal atom from a first location to a second location on the surface of a metal oxide, the method comprising:
(a) obtaining a material having metal atoms deposited on the surface of a metal oxide, wherein a first metal atom is deposited on a first oxygen atom vacancy of the metal oxide; and
(b) transferring the first metal atom on the first oxygen atom vacancy to a second location on the metal oxide by applying a voltage to the first metal atom,
wherein the second location is a second metal atom on a second oxygen atom vacancy of the metal oxide, and wherein the first and second metal atoms form a first metal atom-second metal atom species, or
wherein the second location is a metal atom of the metal oxide, and wherein the first metal atom and the metal atom of the metal oxide forms a first metal atom-metal atom of the metal oxide species.

### Claim 2 (depends on 1)

The method of claim 1, wherein the metal oxide is titanium dioxide and the metal atoms deposited on the surface of the titanium dioxide are gold atoms.

### Claim 3 (depends on 2)

The method of claim 2, wherein the first metal atom-second metal atom species is a Au—Ti species.

### Claim 4 (depends on 2)

The method of claim 2, wherein the first metal atom-metal atom of the metal oxide species is a Au—Ti species.

### Claim 5 (depends on 2)

The method of claim 2, wherein the titanium dioxide is single phase anatase or single phase rutile.

### Claim 6 (depends on 2)

The method of claim 2, wherein the titanium dioxide comprises a mixture of anatase and rutile.

### Claim 7 (depends on 6)

The method of claim 6, wherein the ratio of anatase to rutile ranges from 1.5:1 to 10:1.

### Claim 8 (depends on 6)

The method of claim 6, wherein the titanium dioxide is a mixed phase of anatase and rutile.

### Claim 9 (depends on 1)

The method of claim 1, wherein the voltage ranges from −3.0 V to +3.0.

### Claim 10 (depends on 9)

The method of claim 9, wherein the voltage is pulsed voltage.

### Claim 11 (depends on 9)

The method of claim 9, wherein the voltage is applied for 300 milliseconds to 400 milliseconds at a current of 25 pA to 75 pA.

### Claim 12 (depends on 1)

The method of claim 1, wherein the metal oxide is TiO2, SnO2, Fe2O3, ZnO, or any combination thereof.

### Claim 13 (depends on 1)

The method of claim 1, wherein the metal atoms deposited on the surface of the metal oxide are gold, silver, palladium, rhodium, or platinum atoms.

### Claim 14 (depends on 1)

The method of claim 1, wherein the surface of the metal oxide is reduced.

### Claim 15 (depends on 1)

The method of claim 1, wherein a scanning tunneling microscope (STM) is used in step (b) to transfer the first metal atom on the first oxygen atom vacancy to a second location on the metal oxide by applying a voltage to the first metal atom.

### Claim 16 (depends on 15)

The method of claim 15, wherein the STM has a tungsten tip.

### Claim 17 (depends on 1)

The method of claim 1, wherein a cluster of metal atoms having a targeted size is obtained.

### Claim 18 (depends on 1)

The method of claim 1, wherein the material is a photocatalyst.

### Claim 19 (depends on 1)

A photocatalyst made by a method of claim 1.

### Claim 20 (depends on 1)

A method for designing a photocatalyst comprising selectively obtaining a desired size and/or position of a metal cluster deposited on a metal oxide by using the method of claim 1.