Metal-ligand catalysts for selective promotion of electrochemical CO2RR

Patent metadata

Field	Value
Publication number	US-11697663-B2
Application number	US-202117164281-A
Country	US
Kind code	B2
Filing date	Feb 1, 2021
Priority date	Jan 31, 2020
Publication date	Jul 11, 2023
Grant date	Jul 11, 2023

Abstract

The electrochemical carbon dioxide reduction reaction (CO2RR) provides opportunities to synthesize value-added products from this greenhouse gas in a sustainable manner. Efficient catalysts for this reaction are provided that selectively drive CO2 reduction over the thermodynamic and kinetically competitive hydrogen evolution reaction (HER) in organic or aqueous electrolytes. The catalysts are metal-polypyridyl coordination complexes of a redox non-innocent terpyridine-based pentapyridine ligand and a first-row transition metal. The metal-ligand cooperativity in [Fe(tpyPY2Me)]2+ drives the electrochemical reduction of CO2 to CO at low overpotentials with high selectivity for CO2RR (>90%).

First claim

What is claimed is:

1. A metal coordination complex catalyst, comprising:
(a) a metal; and
(b) a tpyPY2Me ligand represented by formula (1)

wherein each substituent lettered A to S of said ligand is independently selected from the group of substituents consisting of H, R, a halide, CF 3 , OR, NR 2 , and SiR 3 , where R is an alkyl group or an aryl group.

2. The catalyst of claim 1 , further comprising a counter ion selected from the group consisting of Cl, Br, I, PF 6 , CF 3 SO 3 , and [(3,5-(CF 3 ) 2 C 6 H 3 ) 4 B].

3. The catalyst of claim 1 , wherein said metal comprises Fe forming an iron(II) complex [Fe(tpyPY2Me)] 2+ .

4. The catalyst of claim 1 , wherein each substituent lettered A to S comprises a hydrogen atom.

5. The catalyst of claim 1 , wherein said substituents lettered A to S are independently selected from the group of substituents consisting of H, R, OR, NR 2 , and SiR 3 , where R is an alkyl group selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, pentyl, hexyl and cyclohexyl groups.

6. The catalyst of claim 1 , wherein said substituents lettered A to S are independently substituents consisting of H, R, OR, NR 2 , and SiR 3 , where R is an aryl group selected from the group consisting of phenyl, naphthyl, pyridinyl, indolyl and 2-methyl-phenyl groups.

Assignees

• Univ California

Inventors

• Derrick Jeffrey S
• Loipersberger Matthias
• Long Jeffrey R
• Head-Gordon Martin
• Chang Christopher J

Classifications

• B01J31/183

  with more than one complexing nitrogen atom, e.g. phenanthroline · CPC title

• C25B3/26

  of carbon dioxide · CPC title

• C07F15/025 Primary

  without a metal-carbon linkage · CPC title

• B01J31/1815

  with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine · CPC title

• C25B11/073

  characterised by the electrocatalyst material · CPC title