Compounds, their preparation, related compositions, catalysts, electrochemical cells, fuel cells, and uses thereof

Patent metadata

Field	Value
Publication number	US-11142835-B2
Application number	US-201816214088-A
Country	US
Kind code	B2
Filing date	Dec 9, 2018
Priority date	Jun 10, 2016
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

Abstract

In some embodiments, this application relates to inventive compounds (e.g., Formula (I), Formula (II), thiosemicarbazones and/or thiosemicarbazones and their metal (e.g., zinc, cobalt, nickel, or copper) complexes, and extended structures thereof), methods for preparation of the inventive compounds, compositions comprising the inventive compounds (e.g., anode, cathodes, catalysts (e.g., electrocatalysts), glassy carbon electrodes, carbon paste electrodes, covalently modified carbon (e.g., modified graphene)), electrochemical cells comprising compositions that comprise one or more inventive compounds, fuel cells comprising compositions that comprise one or more inventive compounds, uses of one or more inventive compounds to produce H2 (e.g., via an electrochemical cell), and uses of one or more inventive compounds to create energy from H2 (e.g., via a fuel cell). Additional embodiments of the invention are also discussed herein.

First claim

The invention claimed is:

1. A catalyst comprising a composition comprising a compound selected from Formula (I),

and
salts, optical isomers, geometric isomers, salts of isomers, and derivatives thereof, wherein
R 1 is

 or is a monovalent H, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), sulfo (—SO 3 H), halogen, aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 —C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy, which aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy can optionally be substituted with one or more of halogen, hydroxy (—OH), C 1 -C 5 alkyl, C 1 -C 4 alkoxy, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), cyano (—CN), ethynyl (—CCH), sulfo (—SO 3 H), methyl, or ethyl;
X 1 is bivalent —(NH)—, —O—, —(CH 2 )—, or —S—, which —(NH)— or —(CH 2 )— can optionally be substituted with one or more of halogen, hydroxy (—OH), C 1 -C 5 alkyl, C 1 -C 4 alkoxy, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), cyano (—CN), ethynyl (—CCH), sulfo (—SO 3 H), methyl, or ethyl;
R 2 is a monovalent H, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), sulfo (—SO 3 H), halogen, aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy, which aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy can optionally be substituted with one or more of halogen, hydroxy (—OH), C 1 -C 5 alkyl, C 1 -C 4 alkoxy, amine (—NH 2 ), —NR a R b , —N (+) R a R b R c , methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), cyano (—CN), ethynyl (—CCH), sulfo (—SO 3 H), methyl, or ethyl;
R 3 is a monovalent H, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), sulfo (—SO 3 H), halogen, aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy, which aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy can optionally be substituted with one or more of halogen, hydroxy (—OH), C 1 -C 5 alkyl, C 1 -C 4 alkoxy, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), cyano (—CN), ethynyl (—CCH), sulfo (—SO 3 H), methyl, or ethyl;
R 4 is a monovalent H, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), sulfo (—SO 3 H), halogen, aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy, which aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy can optionally be substituted with one or more of halogen, hydroxy (—OH), C 1 -C 5 alkyl, C 1 -C 4 alkoxy, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), cyano (—CN), ethynyl (—CCH), sulfo (—SO 3 H), methyl, or ethyl;
R 5 is

or is a monovalent H, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), sulfo (—SO 3 H), halogen, aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy, which aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy can optionally be substituted with one or more of halogen, hydroxy (—OH), C 1 -C 5 alkyl, C 1 -C 4 alkoxy, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), cyano (—CN), ethynyl (—CCH), sulfo (—SO 3 H), methyl, or ethyl;
X 2 is bivalent —(NH)—, —O—, —(CH 2 )—, or —S—, which —(NH)— or —(CH 2 )— can optionally be substituted with one or more of halogen, hydroxy (—OH), C 1 -C 5 alkyl, C 1 -C 4 alkoxy, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), cyano (—CN), ethynyl (—CCH), sulfo (—SO 3 H), methyl, or ethyl; R 6 is a monovalent H, methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), sulfo (—SO 3 H), halogen, aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy, which aryl, cycloalkyl, heterocyclyl, heteroaryl, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, or C 1 -C 6 alkoxy can optionally be substituted with one or more of halogen, hydroxy (—OH), C 1 -C 5 alkyl, C 1 -C 4 alkoxy, amine (—NH 2 ), —NR a R b , —N (+) R a R b R c , methanoly (—COH), carboxy (—CO 2 H), nitro (—NO 2 ), cyano (—CN), ethynyl (—CCH), sulfo (—SO 3 H), methyl, or ethyl; R a , R b , and R c are each independently selected from C 1 -C 5 alkyl; and the compound is not

2. The catalyst of claim 1 , wherein
(a) R 3 is the same as R 4 ;
(b) R 3 is the same as R 4 and R 1 is the same as R 5 ;
(c) R 3 is the same as R 4 , X 1 is —(NH)—, X 2 is —(NH)—, and R 2 is the same as R 6 ;
(d) R 3 is the same as R 4 , R 3 is methyl, R 1 is the same as R 5 , R 1 is

X 1 is —(NH)—, and R 2 is —CH 3 ;
(e) R 3 is the same as R 4 , R 3 is methyl, R 1 is the same as R 5 , R 1 is

X 1 is —(NH)—, and R 2 is —C 5 H 6 ;
(f) R 3 is the same as R 4 , R 3 is methyl, R 1 is the same as R 5 , R 1 is

X 1 is —(NH)—, and R 2 is —CH 2 F 3 ;
(g) R 3 is the same as R 4 , R 3 is methyl, R 1 is the same as R 5 , R 1 is

X 1 is —(NCH 3 )—, and R 2 is —CH 3 ;
(h) R 3 is the same as R 4 , R 3 is methyl, R 1 is the same as R 5 , R 1 is

X 1 is —O—, and R 2 is —CH 3 ;
(i) R 3 is the same as R 4 and R 3 is methyl;
(j) R 3 is the same as R 4 and R 3 is ethyl;
(k) R 3 is methyl and R 4 is phenyl;
(l) R 1 is

X 1 is —(NH)—, R 2 is —CH 3 , R 5 is

X 2 is —(N—CH(CH 3 ) 2 )—, and R 6 is —CH(CH 3 ) 2 ;
(m) R 1 is

X 1 is —(NH)—, R 2 is —CH 3 , R 5 is

X 2 is —(NH)—, and R 6 is —C 5 H 6 ;
(n) R 1 is

X 1 is —(NH)—, R 2 is —CH 3 , R 5 is

X 2 is —(NH)—, and R 6 is —CH 2 CF 3 ;
(o) R 1 is

X 1 is —(NH)—, R 2 is —CH 3 , R 5 is

X 2 is —O—, and R 6 is —CH 3 ;
(p) R 1 is

X 1 is —(NH)—, R 2 is —CH 3 , R 5 is

Assignees

• Univ Louisville Res Found Inc

Inventors

• Grapperhaus Craig A
• Buchanan Robert M
• Haddad Andrew Z
• Calvary Caleb Aaron

Classifications

• C25B11/095

  at least one of the compounds being organic · CPC title

• C07F15/045

  without a metal-carbon linkage · CPC title

• C25B11/075

  consisting of a single catalytic element or catalytic compound · CPC title

• Y02E60/36

  Hydrogen production from non-carbon containing sources, e.g. by water electrolysis · CPC title

• C25B11/04 Primary

  characterised by the material · CPC title