# US 10,119,197 B2 · Solar water splitting in a molecular photoelectrochemical cell

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- Number: US 10,119,197 B2
- Document ID: US10119197B2
- Status: Granted
- Kind: B2
- Application number: 14/479,995
- Filed: 2014-09-08
- Published: 2015-03-12
- Granted: 2018-11-06
- Earliest claimed: 2013-09-07
- Assignees: The University of North Carolina at Chapel Hill; North Carolina State University
- Applicants: The University of North Carolina at Chapel Hill; North Carolina State University
- Inventors: Leila Alibabaei; Matthew Kyle Brennaman; Michael Norris; Gregory N. Parsons; Thomas J. Meyer
- Web page: https://patentgrep.com/patent/US10119197B2

## CPC

- C25B 11/077: the compound being a non-noble metal oxide
- C25B 1/55: Photoelectrolysis
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- Y02P 20/133: Renewable energy sources, e.g. sunlight
- C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A Dye Sensitized Photoelectrosynthesis Cell (DSPEC) splits water with visible light using a derivatized, core/shell nanostructured photoanode with the core having a high surface area conductive metal oxide film—such as nanoITO (indium tin oxide) or nanoATO (antimony tin oxide)—coated with a thin outer shell of, for example, TiO2 formed by Atomic Layer Deposition (ALD). A “chromophore-catalyst assembly” 1, [(PO3H2)2bpy)2Ru(4-Mebpy-4-bimpy)Ru(tpy)(OH2)]4+, which combines both light absorber and water oxidation catalyst in a single molecule, is attached to the TiO2 shell. Visible photolysis of the resulting core/shell/assembly structure with a Pt cathode results in water splitting into hydrogen and oxygen.

## Claims

### Claim 1

A photoharvesting complex comprising:
a transparent conductive metal oxide core;
a metal oxide shell having a thickness not greater than about 5 nm, wherein the metal oxide shell comprises TiO2;
a first molecule chromophore; and
a second molecule catalyst.

### Claim 2 (depends on 1)

The photoharvesting complex of claim 1, wherein the transparent conductive metal oxide core is chosen from tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony tin oxide (ATO), gallium zinc oxide (GZO), indium zinc oxide (IZO), copper aluminum oxide, fluorine-doped zinc oxide, and aluminum zinc oxide, and combinations thereof.

### Claim 3 (depends on 1)

The photoharvesting complex of claim 1, wherein the first molecule chromophore is chosen from ruthenium coordination complexes, osmium coordination complexes, copper coordination complexes, porphyrins, phythalocyanines, and organic dyes, and combinations thereof.

### Claim 4 (depends on 1)

The photoharvesting complex of claim 1, wherein the second molecule catalyst is chosen from transition metal catalysts.

### Claim 5 (depends on 4)

The photoharvesting complex of claim 4, wherein the transition metal catalyst is chosen from iron catalysts, ruthenium catalysts, osmium catalysts, and combinations thereof.

### Claim 6 (depends on 1)

The photoharvesting complex of claim 1, wherein the transparent conductive metal oxide core comprises nanoparticles of a transparent conductive metal oxide.

### Claim 7 (depends on 6)

The photoharvesting complex of claim 6, wherein the nanoparticles have an average size of less than about 1 μm.

### Claim 8 (depends on 6)

The photoharvesting complex of claim 6, wherein the nanoparticles have an average size of less than about 50 nm.

### Claim 9 (depends on 6)

The photoharvesting complex of claim 6, wherein the nanoparticles have an average size of less than about 25 nm.

### Claim 10 (depends on 6)

The photoharvesting complex of claim 6, wherein the nanoparticles have an average size of less than about 10 nm.

### Claim 11 (depends on 1)

The photoharvesting complex of claim 1, wherein the transparent conductive metal oxide core comprises from tin-doped indium oxide (ITO), antimony tin oxide (ATO), or a combination thereof.

### Claim 12 (depends on 11)

The photoharvesting complex of claim 11, wherein the transparent conductive metal oxide core comprises tin-doped indium oxide (ITO).

### Claim 13 (depends on 11)

The photoharvesting complex of claim 11, wherein the transparent conductive metal oxide core comprises antimony tin oxide (ATO).