Nickel-based catalysts for C=O reduction and oxygen evolution

Patent metadata

Field	Value
Publication number	US-10654879-B2
Application number	US-201715723998-A
Country	US
Kind code	B2
Filing date	Oct 3, 2017
Priority date	Oct 3, 2016
Publication date	May 19, 2020
Grant date	May 19, 2020

Abstract

A compound having formula I that is useful for C═O reduction is provided:

wherein:

M is a transition metal;

X 1 , X 2 are each independently a counterion; and

R 1 , R 2 , R 3 are each independently H, C 1-6 alkyl, C 6-15 aryl, or C 6-15 heteroaryl.

First claim

What is claimed is:

1. A compound having formula I:

wherein:
M is a transition metal;
X 1 , X 2 are each independently a counterion; and
R 1 , R 2 , R 3 are each independently H, C 1-6 alkyl, C 6-15 aryl, or C 6-15 heteroaryl.

2. The compound of claim 1 wherein M is a metal selected from the group consisting of beryllium, magnesium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thallium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, gold, platinum, thallium, lead, bismuth, polonium, thorium, protactinium, uranium, neptunium, and plutonium.

3. The compound of claim 1 wherein M is nickel.

4. The compound of claim 1 wherein X 1 is a hydride or a borate group (BH 2 − ) and X 2 is F, Cl, Br, I, tosylate, or mesylate.

5. The compound of claim 1 wherein R 1 , R 2 , R 3 are each independently H.

6. A compound having formula II:

wherein:
R 5 , R 6 , R 7 , R 8 , R 9 are each independently H, C 1-6 alkyl, C 6-15 aryl, or C 6-15 heteroaryl; and
M is a transition metal.

7. The compound of claim 6 wherein M is a metal selected from the group consisting of beryllium, magnesium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thallium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, gold, platinum, thallium, lead, bismuth, polonium, thorium, protactinium, uranium, neptunium, and plutonium.

8. The compound of claim 6 wherein M is nickel.

9. The compound of claim 6 wherein R 8 , R 9 are each independently H.

10. The compound of claim 6 wherein R 5 are each independently methyl or mesityl.

11. The compound of claim 6 wherein R 5 are each independently methyl or mesityl.

12. The compound of claim 6 wherein R 6 , R 7 are each independently H or methyl.

13. An electrochemically active substrate formed by a method comprising: contacting a metallic substrate with a compound having formula I or II:

wherein:
M is a transition metal;
X 1 , X 2 are each independently a counterion; and
R 1 , R 2 , R 3 are each independently H, C 1-6 alkyl, C 6-15 aryl, or C 6-15 heteroaryl;
R 5 , R 6 , R 7 , R 8 , R 9 are each independently H, C 1-6 alkyl, C 6-15 aryl, or C 6-15 heteroaryl.

14. The electrochemically active substrate of claim 13 wherein the metallic substrate includes nickel.

15. An electrochemical cell comprising the electrochemically active substrate of claim 13 and a counter-electrode.

16. The electrochemical cell of claim 15 further comprising an electrolyte disposed between the electrochemically active substrate and the counter-electrode.

17. The electrochemical cell of claim 16 further comprising a voltage source that applies a voltage across the electrochemical cell such that O 2 is converted to H 2 O when the electrochemically active substrate is contacted with O 2 .

18. The electrochemical cell of claim 17 further comprising a voltage source that applies a voltage across the electrochemical cell such that H 2 O is converted to O 2 when the electrochemically active substrate is contacted with H 2 O.

19. A method comprising: contacting a compound having formula I or II with carbon dioxide to form methanol:

wherein:
M is a transition metal;
X 1 , X 2 are each independently a counterion; and
R 1 , R 2 , R 3 are each independently H, C 1-6 alkyl, C 6-15 aryl, or C 6-15 heteroaryl;
R 5 , R 6 , R 7 , R 8 , R 9 are each independently H, C 1-6 alkyl, C 6-15 aryl, or C 6-15 heteroaryl.

20. A compound having formula III:

wherein:
M is a transition metal; and
R 1 , R 2 , R 3 are each independently H, C 1-6 alkyl, C 6-15 aryl, or C 6-15 heteroaryl.

Assignees

• Univ Southern California

Inventors

• Narayan Sri
• Williams Travis J
• Lu Zhiyao
• Mitra Debanjan

Classifications

• C07F15/04 Primary

  Nickel compounds · CPC title

• C07C29/147

  of carboxylic acids or derivatives thereof · CPC title

• C07C29/159

  with reducing agents other than hydrogen or hydrogen-containing gases · CPC title

• C07C29/157

  containing platinum group metals or compounds thereof · CPC title

• C07F15/045

  without a metal-carbon linkage · CPC title