Use of acidic electrolyte cations for selective electrochemical co2 and co conversions to methanol

Abstract

Described is a method is to improve catalytic activity and selectivity for electrochemical CO2-to-methanol and CO-to-methanol conversions by employing acidic electrolyte cations that can facilitate proton transfer during the electrocatalytic conversion reactions.

1 . A method of producing methanol, comprising:
 contacting an aqueous solution comprising a cation and an anion with CO 2  or CO, thereby forming an aqueous solution comprising a cation, an anion, and CO 2  or CO;   contacting the aqueous solution comprising the cation, the anion, and CO 2  or CO with an electrode (RHE); and   applying a voltage to the aqueous solution comprising the cation, the anion, and CO 2  or CO via the electrode.   
     
     
         2 . The method of  claim 1 , wherein the cation is a metal cation. 
     
     
         3 . The method of  claim 2 , wherein the metal cation is an alkali metal or an alkaline-earth metal. 
     
     
         4 . The method of  claim 2 , wherein the metal cation is selected from the group consisting of Li + , Nat, K + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , and Ba 2+ ; or a combination thereof. 
     
     
         5 - 8 . (canceled) 
     
     
         9 . The method of  claim 1 , wherein the cation is an ammonium cation. 
     
     
         10 . The method of  claim 1 , wherein the cation is an alkylammonium cation. 
     
     
         11 . (canceled) 
     
     
         12 . The method of  claim 1 , wherein the anion is bicarbonate or hydroxide. 
     
     
         13 . The method of  claim 1 , wherein the anion is phosphate, boronate, or sulphate. 
     
     
         14 . The method of  claim 1 , wherein the method is performed at about pH 2, about pH 3, about pH 4, about pH 5, about pH 6, about pH 7, about pH 8, about pH 9, about pH 10, about pH 11, about pH 12, or about pH 13. 
     
     
         15 . The method of  claim 1 , wherein the method is performed at about pH 6.8 or about pH 13. 
     
     
         16 . (canceled) 
     
     
         17 . (canceled) 
     
     
         18 . The method of  claim 1 , wherein the voltage is applied vs. a reference hydrogen electrode (RHE) (i.e., V RHE ). 
     
     
         19 . The method of  claim 1 , wherein the voltage is applied at about −0.5 V RHE , about −0.6 V RHE , about −0.7 V RHE , about −0.8 V RHE , about −0.9 V RHE , or about −1.0 V RHE . 
     
     
         20 - 27 . (canceled) 
     
     
         28 . The method of  claim 1 , wherein the electrode comprises CoPc. 
     
     
         29 - 31 . (canceled) 
     
     
         32 . The method of  claim 28 , wherein the CoPc is ligated to a ligand comprising amino, nitrogen, alkyl, carboxyl, or halo. 
     
     
         33 . The method of  claim 1 , wherein the method has a selectivity of methanol vs. carbon monoxide at greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% in favor of methanol. 
     
     
         34 . The method of  claim 1 , wherein the method has a selectivity of methanol vs. carbon monoxide at greater than 30% in favor of methanol. 
     
     
         35 . The method of  claim 1 , wherein the method has a selectivity of methanol vs. carbon monoxide of about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% in favor of methanol. 
     
     
         36 . The method of  claim 1 , wherein the method has a selectivity of methanol vs. carbon monoxide of about 30% in favor of methanol. 
     
     
         37 . The method of  claim 1 , wherein the method comprises:
 contacting an aqueous solution comprising a metal cation and an anion with CO 2 , thereby forming an aqueous solution comprising a cation, an anion, and CO 2 ;   contacting the aqueous solution comprising the cation, the anion, and CO 2  with an electrode; and   applying a voltage to the aqueous solution comprising the cation, the anion, and CO 2  via the electrode.   
     
     
         38 . The method of  claim 1 , wherein the method comprises:
 contacting an aqueous solution comprising a metal cation and an anion with CO, thereby forming an aqueous solution comprising a cation, an anion, and CO;   contacting the aqueous solution comprising the cation, the anion, and CO with an electrode; and   applying a voltage to the aqueous solution comprising the cation, the anion, and CO via the RHE.   
     
     
         39 - 46 . (canceled)