# US 11,028,490 B2 · Subnanometer catalytic clusters for water splitting, method for splitting water using subnanometer catalyst clusters

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- Number: US 11,028,490 B2
- Document ID: US11028490B2
- Status: Granted
- Kind: B2
- Application number: 16/043,322
- Filed: 2018-07-24
- Published: 2019-01-17
- Granted: 2021-06-08
- Earliest claimed: 2013-04-12
- Assignees: Uchicago Argonne, LLC
- Applicants: Uchicago Argonne, LLC
- Inventors: Stefan Vajda; Larry A. Curtiss; Michael J. Pellin
- Web page: https://patentgrep.com/patent/US11028490B2

## CPC

- C25B 11/02: characterised by shape or form
- C25B 1/04: by electrolysis of water
- C25B 3/25: Reduction
- C25B 3/26: of carbon dioxide
- C25B 11/051: Electrodes formed of electrocatalysts on a substrate or carrier
- C25B 11/057: consisting of a single element or compound
- C25B 11/059: Silicon
- C25B 11/069: consisting of at least one single element and at least one compound; consisting of two or more compounds
- C25B 11/077: the compound being a non-noble metal oxide
- C25B 11/081: the element being a noble metal
- C25B 11/083: Diamond
- C25B 11/091: consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B 3/03: Acyclic or carbocyclic hydrocarbons
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- 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

## Abstract

The invention provides a catalytic electrode for converting molecules, the electrode comprising a predetermined number of single catalytic sites supported on a substrate. Also provided is a method for oxidizing water comprising contacting the water with size selected catalyst clusters. The invention also provides a method for reducing an oxidized moiety, the method comprising contacting the moiety with size selected catalyst clusters at a predetermined voltage potential.

## Claims

### Claim 1

A method for splitting water comprising:
a) contacting the water with a catalytic electrode of an electrocatalytic cell, wherein the electrocatalytic cell comprises the catalytic electrode, an alkaline electrolyte with a pH greater than 10, and a reference hydrogen electrode, wherein the two electrodes and electrolyte are all in fluid communication, and wherein the catalytic electrode comprises a wafer coated with (ultra)nanocrystalline diamond so as to define a surface supporting catalyst spots, each spot consisting only of a plurality of palladium clusters, wherein each of the clusters have a size of between 3 and 20 atoms and remain physically isolated from each other, wherein each cluster spot is between 4 and 5 mm in diameter wherein the size of all the plurality of palladium clusters is selected from the group consisting of 4 plus or minus 1, 6 plus or minus 2, and 17 plus or minus 3 atoms of palladium per cluster; and
b) applying a voltage to the electrodes.

### Claim 2 (depends on 1)

The method as recited in claim 1 wherein the (ultra)nanocrystalline diamond overlays a foundation material.

### Claim 3 (depends on 1)

The method as recited in claim 1 wherein the wafer comprises silicon.

### Claim 4 (depends on 1)

The method of claim 1 wherein the voltage is between approximately −2 V and +2.5V.

### Claim 5 (depends on 4)

The method of claim 4 wherein the catalytic electrode is catalytically active at temperatures ranging between approximately 5° C. and 900° C.

### Claim 6 (depends on 5)

The method of claim 5 wherein the clusters do not dissolve into smaller clusters or agglomerate into larger clusters.

### Claim 7 (depends on 1)

The method of claim 1 wherein wafer coverage by the clusters is about 0.1 atomic ML equivalent of palladium metal.

### Claim 8 (depends on 1)

The method of claim 1 wherein each of the clusters size-selected to comprise 4 plus or minus 1 palladium atoms have a turnover rate of about −0.15 cluster−1 second−1.

### Claim 9 (depends on 1)

The method of claim 1 wherein each of the clusters size-selected to comprise 6 plus or minus 2 palladium atoms have a turnover rate of about 4.03 cluster−1second−1.

### Claim 10 (depends on 1)

The method of claim 1 wherein each of the clusters size-selected to comprise 17 plus or minus 3 palladium atoms have a turnover rate of about 10.17 cluster−1second−1.

### Claim 11 (depends on 6)

The method of claim 6 wherein the clusters are in fluid communication.