The University of North Carolina at Chapel Hill

Gas Research Institute

North Carolina State University

The United States of America As Represented by the Department of Health

Los Alamos National Security, LLC

Thomas J Meyer

Paul G Hoertz

Royce W Murray

Javier Jesus Concepcion Corbea

Jonah Wesley Jurss

Joseph L Templeton

William J Vining

B Patrick Sullivan

T David Westmoreland

Lawrence D Margerum

Terrence R O'Toole

Zuofeng Chen

David A Wink

Victor I Klimov

Janet N Younathan

Gregory N Parsons

Milan Sykora

Tadeusz Malinski

Danae D Christodoulou

Poonam M Narula

Michael Norris

Melani Sullivan

Leila Alibabaei

Zoufeng Chen

Matthew Kyle Brennaman

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&#x2014;such as nanoITO (indium tin oxide) or nanoATO (antimony tin oxide)&#x2014;coated with a thin outer shell of, for example, TiOformed by Atomic Layer Deposition (ALD). A 'chromophore-catalyst assembly' 1, [(POH)bpy)Ru(4-Mebpy-4-bimpy)Ru(tpy)(OH)], which combines both light absorber and water oxidation catalyst in a single molecule, is attached to the TiOshell. Visible photolysis of the resulting core/shell/assembly structure with a Pt cathode results in water splitting into hydrogen and oxygen.

Solar water splitting in a molecular photoelectrochemical cell

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

Photocatalytic materials based on coupling of semiconductor nanocrystalline quantum dots (NQD) and molecular catalysts. These materials have capability to drive or catalyze non-spontaneous chemical reactions in the presence of visible radiation, ultraviolet radiation, or both. The NQD functions in these materials as a light absorber and charge generator. Following light absorption, the NQD activates a molecular catalyst adsorbed on the surface of the NQD via transfer of one or more charges (either electrons or electron-holes) from the NQD to the molecular catalyst. The activated molecular catalyst can then drive a chemical reaction. A photoelectrolytic device that includes such photocatalytic materials is also described.

Activation of molecular catalysts using semiconductor quantum dots

Concentration of tritium and/or deuterium that is a contaminant in H,O, followed by separation of the concentrate from the H,O. Employed are certain metal oxo complexes, preferably with a metal from Group VIII. For instance, &lsqb;Ru,(2,2&prime;,6&prime;,2&Prime;-terpyridine)(2,2&prime;-bipyridine)(O)&rsqb;(ClO,),is very suitable.

Concentration and removal of tritium and/or deuterium from water contaminated with tritium and/or deuterium

An electrode sensor which may be used to specifically and quantitatively measure nitric oxide is provided, as well as a method of preparing and using such an electrode sensor to measure nitric oxide concentration in solution. A nitric oxide (NO) microsensor based on catalytic oxidation of NO comprises a thermally-sharpened carbon fiber with a tip diameter of about 0.5-0.7 .mu.m coated with several layers of p-type semiconducting polymeric porphyrin and cationic exchanger deposited thereon. The microsensor, which can be operated in either the amperometric, voltammetric or coulometric mode utilizing a two or three electrode system, is characterized by a linear response up to about 300 .mu.M, a response time better than 10 msec and a detection limit of about 10 nM. The sensor of the present invention also discriminates against nitrite, the most problematic interferant in NO measurements. The amount of NO released from a single cell can thus be selectively measured in situ by a porphyrinic microsensor of the invention. A larger scale sensor utilizing porphyrin and cationic exchanger deposited on larger fibers or wires, platinum mesh or tin indium oxide layered on glass, can also be employed when measurement of NO concentration in chemical media, tissue or cell culture is desired.

Nitric oxide sensor

An electrode that has a film adsorbed to its surface by reductive electropolymerization of (vbpy)Re(CO).sub.3 Cl (4-vinyl-4'-methyl-2,2'-bipyridine tricarbonylchlororhenium(I)) or its acetonitrile analogue, [(vbpy)Re(CO).sub.3 (MeCN)].sup.+ (4-vinyl-4'-methyl-2,2'-bipyridine tricarbonylacetonitrile rhenium (I)). The poly(vbpy)Re(CO).sub.3 Cl or poly[(vbpy)Re(CO).sub.3 (MeCN)].sup.+ adsorbed onto the electrode, acts as a catalyst for CO.sub.2 reduction to CO. Stability and the reactivity of the polymer film may be increased by co-reductive electropolymerization of either of the aforesaid Re complexes with [(bpy).sub.2 Ru(vpy).sub.2.sup.2+ (bis(4-vinyl-pyridine)bis(2,2'-bipyridine) ruthenium (II)) (vpy is 4-vinylpyridine). A bilayer film assembly consisting of poly-[(bpy).sub.2 Ru(vpy).sub.2 ].sup.2+ as an inner film and the aforementioned copolymer of Ru/Re yields even greater reactivity to CO.sub.2. A method of forming a polymeric film on an electrode. A method of reducing CO.sub.2 to CO using an electrode having a polymeric film adsorbed to its surface.

Chemically modified electrodes for the catalytic reduction of CO.sub.2

An electrode that has a film adsorbed to its surface by reductive electropolymerization of (vbpy)Re(CO).sub.3 Cl (4-vinyl-4'-methyl-2,2'-bipyridine tricarbonylchlororhenium(I)) or its acetonitrile analogue, [(vbpy)Re(CO).sub.3 (MeCN)].sup.+ (4-vinyl-4'-methyl-2,2'-bipyridine tricarbonylacetonitrile rhenium (I)). The poly (vbpy)Re(CO).sub.3 Cl or poly-[(vbpy)Re(CO).sub.3 (MeCN)].sup.+ adsorbed onto the electrode, acts as a catalyst for CO.sub.2 reduction to CO. Stability and the reactivity of the polymer film may be increased by co-reductive electropolymeriaztion of either of the aforesaid Re complexes with [(bpy).sub.2 Ru(vpy).sub.2.sup.2+ ](bis(4-vinyl-pyridine)bis(2,2'-bipyridine) ruthenium (II)) (vpy is 4-vinylpyridine). A bilayer film assembly consisting of poly-[(bpy).sub.2 Ru(vpy).sub.2 ].sup.2+ as an inner film and the aforementioned copolymer of Ru/Re yields even greater reactivity to CO.sub.2. A method of forming a polymeric film on an electrode. A method of reducing CO.sub.2 to CO using an electrode having a polymeric film adsorbed to its surface.

Growing community of inventors

Chapel Hill, NC, United States of America

Thomas J Meyer