Electrocatalytic co2 or co reduction

A method for reducing carbon dioxide comprising:

• electrolytically reducing carbon dioxide in the presence of a compound that includes an organometallic complex having formula 1 and one or more counterions Xn(− or +)if the formal charge of the organometallic complex is not zero:
• wherein:
• M is a transition metal;
• Z is S, O, Se, Te, or NH;
• n(+ or −) is the formal charge of the organometallic complex;
• n(− or +) is the formal charge of the one or more counterions that balances the formal charge of the organometallic complex;
• and
• L is an optional ligand or an optional donor group from another ligand attached to M;
• and R1, R2, R3, R4, R5, R6, R7 and R8 are each independently C1-10 alkyl, C6-10 cycloalkyl, or C6-14 aryl with the proviso that any 2 of R1, R2, R3, R4 can be bonded together to form a multidentate ligand.

An electrochemical cell for converting carbon monoxide to a value-added product, the electrochemical cell comprising:

• a vessel;
• a liquid electrolyte disposed in the vessel;
• a cathode at least partially immersed in the electrolyte;
• an anode at least partially immersed in the electrolyte;
• a carbon monoxide source for providing carbon monoxide to the electrolyte;
• a power supply for biasing the cathode relative to the anode;
• and
• an organometallic complex having formula 4 and one or more counterions Xn(− or +) if the formal charge of the organometallic complex is not zero:
• wherein:
• M is a transition metal;
• Z is S, O, Se, Te, or NH;
• n(+ or −) is the formal charge of the organometallic complex;
• n(− or +) is the formal charge of the one or more counterions that balances the formal charge of the organometallic complex;
• is an integer from 0 to 4;
• and
• R9, R10, are each independently C1-10 alkyl or C6-14 aryl;
• and
• R11 is C1-6 alkyl, C6-10 aryl, C6-10 cycloalkyl, C6-10 heteroaryl, —NO2, —NH2, —N(R′R″), —N(R′R″R′″)+L−, Cl, F, Br, —CF3, —CCl3, —CN, —SO3H, —PO3H2, —COOH, —CO2R′, —COR′, —CHO, —OH, —OR′, —O−M′+, —SO3−M′+, —PO3−M′+, —COO−M′+, —CF2H, —CF2R′, —CFH2, and —CFR′R″ where R′, R″ and R′″ are C1-10 alkyl or C6-18 aryl groups, L− is a negatively charged counter ion, and M′+ is a metal cation.

A method for reducing carbon monoxide comprising:

• electrolytically reducing carbon monoxide in the presence of a compound that includes an organometallic complex having formula 4 and one or more counterions Xn(− or +) if the formal charge of the organometallic complex is not zero:
• wherein:
• M is a transition metal;
• Z is S, O, Se, Te, or NH;
• n(+ or −) is the formal charge of the organometallic complex;
• n(− or +) is the formal charge of the one or more counterions that balances the formal charge of the organometallic complex;
• o is an integer from 0 to 4;
• R9, R10, R11 are each independently C1-10 alkyl or C6-14 aryl;
• and
• R11 is C1-6 alkyl, C6-10 aryl, C6-10 cycloalkyl, C6-10 heteroaryl, —NO2, —NH2, —N(R′R″), —N(R′R″R′″)+L−, Cl, F, Br, —CF3, —CCl3, —CN, —SO3H, —PO3H2, —COOH, —CO2R′, —COR′, —CHO, —OH, —OR′, —O−M′+, —SO3−M′+, —PO3−M′+, —COO−M′+, —CF2H, —CF2R′, —CFH2, and —CFR′R″ where R′, R″ and R′″ are C1-10 alkyl or C6-18 aryl groups, L− is a negatively charged counter ion, and M′+ is a metal cation.