Electrochemical generation of carbon-containing products from carbon dioxide and carbon monoxide

Abstract

Disclosed herein is a method of electroreduction with a working electrode and counter electrode. The method includes a step of electrocatalyzing carbon monoxide and/or carbon dioxide in the presence of one or more nucleophilic co-reactants in contact with a catalytically active material present on the working electrode, thereby forming one or more carbon-containing products electrocatalytically.

1 - 20 . (canceled) 
     
     
         21 . A method of producing a carbon-containing product comprising steps of:
 providing a flow electrolyzer comprising:   (i) an anode having a first anode side and a second anode side,   (ii) a cathode having a first cathode side and a second cathode side,   (iii) a porous membrane between the first anode side and the second cathode side having a first membrane side and a second membrane side,   (iv) a first fluid chamber in contact with the first cathode side,   (v) an anolyte chamber in contact with the first anode side, the second anode side, or both the first anode side and the second membrane side, and   (vi) an optional catholyte chamber in contact with the second cathode side, or in contact with both the second cathode side and the first membrane side,   providing an electricity source, wherein the anode and the cathode are electrically connected to the electricity source;   providing a CO stream consisting essentially of carbon monoxide;   providing an anolyte stream comprising a first electrolyte;   optionally providing a catholyte stream comprising a second electrolyte;   providing a nucleophilic co-reactant stream comprising one or more nucleophilic co-reactants;   concurrently flowing the CO stream into the first fluid chamber, the anolyte stream into the anolyte chamber, the nucleophilic co-reactant stream into either (i) the first fluid chamber or the anolyte chamber, or (ii) if the catholyte chamber is present, the first fluid chamber, the anolyte chamber or the catholyte chamber, and, optionally, the catholyte stream, if present, into the catholyte chamber, if present, and;   providing an electric current from the electricity source through the anode to the cathode to generate the carbon-containing product; and   withdrawing a stream of the carbon-containing product from the flow electrolyzer.   
     
     
         22 . The method of  claim 21 , wherein the one or more nucleophilic co-reactants comprise one or more nucleophilic functional groups per molecule each bearing at least one active hydrogen. 
     
     
         23 . The method of  claim 22 , wherein the one or more nucleophilic functional groups are selected from the group consisting of hydroxyl, thiol, carboxyl, primary amino and secondary amino. 
     
     
         24 . The method of  claim 23 , wherein the one or more nucleophilic co-reactants are selected from the group consisting of ammonia, amines, alcohols, carboxylic acids and thiols. 
     
     
         25 . The method of  claim 24 , wherein the one or more nucleophilic co-reactants are selected from the group consisting of C 1 -C 6  aliphatic primary amines, C 1 -C 6  aliphatic secondary amines, aromatic primary amines, and aromatic secondary amines. 
     
     
         26 . The method of  claim 21 , wherein the carbon-containing product comprises one or more of acetic acid, acetate, acetaldehyde, an amide and a thioester. 
     
     
         27 . The method of  claim 21 , wherein the flow electrolyzer comprises the catholyte chamber. 
     
     
         28 . The method of  claim 27 , wherein the catholyte stream is present, and comprising the step of concurrently flowing the catholyte stream into the catholyte chamber, the CO stream into the first fluid chamber, the anolyte stream into the anolyte chamber, and the nucleophilic co-reactant stream into one of the first fluid chamber, the anolyte chamber or the catholyte chamber. 
     
     
         29 . The method of  claim 21 , wherein the cathode comprises a cathodic catalytically active material comprised of at least one of copper, a copper oxide, and a copper-containing material. 
     
     
         30 . The method of  claim 29 , wherein the cathodic catalytically active material is present on a carbon support or a conductive support which is dispersed in an ion conducting polymer and/or a hydrophobic polymer and deposited on a porous gas diffusion layer or porous membrane material. 
     
     
         31 . The method of  claim 21 , wherein the anode comprises an anodic catalytically active material comprised of at least one metal selected from the group consisting of iridium, nickel, iron, and tin. 
     
     
         32 . The method of  claim 31 , wherein the at least one metal is present, at least in part, as a metal oxide. 
     
     
         33 . The method of  claim 21 , wherein the anode comprises one or more of Ir/IrO 2 , NiO, Co 3 O 4 , Fe—NiO x , RuO 2 , MnO 2 , Mn 2 O 3 , and Co—PO x . 
     
     
         34 . The method of  claim 21 , wherein the anode is metal-free. 
     
     
         35 . The method of  claim 34 , wherein the anode comprises conductive carbon, graphitic carbon, graphene, and functionalized graphene-based materials. 
     
     
         36 . The method of  claim 21 , wherein the first electrolyte and the second electrolyte individually comprise a metal salt comprising at least one metal cation and at least one anion selected from the group consisting of carbonate, bicarbonate, halides and hydroxide. 
     
     
         37 . The method of  claim 36 , wherein the metal salt is an alkali metal salt. 
     
     
         38 . The method of  claim 37 , wherein the anolyte stream comprises at least one of potassium hydroxide and potassium chloride. 
     
     
         39 . The method of  claim 21 , conducted under basic conditions. 
     
     
         40 . The method of  claim 39 , wherein the anolyte stream is basic. 
     
     
         41 . The method of  claim 21 , wherein the anolyte stream has a measurable pH in a range of 2 to 4. 
     
     
         42 . The method of  claim 21 , wherein the porous membrane comprises at least one of an anion exchange membrane, a cation exchange membrane, and a bipolar membrane.