Electroreduction of carbon dioxide on transition metal oxide catalysts

Abstract

Provided is a method for the electrolytic reduction of CO2 that comprises providing an electrolytic cell comprising at least one reaction chamber comprising at least one anode and at least one cathode placing at least one electrolyte solution between at least one anode and at least one cathode, wherein the at least one cathode comprises at least one catalyst surface comprising at least one transition metal oxide, providing CO2 in the electrolyte solution; and applying electrical potential to the electrolytic cell, so that CO2 undergoes at least one reduction reaction at the cathode to provide at least one product selected from the group consisting of methanol, methane, mcthanediol and formic acid. Also provided is an electrochemical dev ice for electrochemical reduction of CO2 that has at least one cathode comprising a transition metal oxide.

1 . A method for the electrolytic reduction of CO 2 , the method comprising:
 providing an electrolytic cell comprising at least one reaction chamber comprising at least one anode and at least one cathode, wherein the at least one cathode comprises at least one catalyst surface comprising at least one transition metal oxide selected from the group consisting of HfO 2 , OsO 2 , RhO 2 , CrO 2 , NbO 2 , MnO 2 , ZrO 2 , and VO 2 ;   placing at least one electrolyte solution between the at least one anode and the at least one cathode, so that the at least one anode and the at least one cathode come into contact with the electrolyte solution;   providing CO 2  in the electrolyte solution; and   applying electrical potential to the electrolytic cell;   whereby CO 2  undergoes at least one reduction reaction at the cathode to provide methanol, or formic acid.   
     
     
         2 . The method of  claim 1 , wherein the at least one transition metal oxide is selected from the group consisting of HfO 2 , NbO 2 , and ZrO 2 . 
     
     
         3 . The method of  claim 1 . wherein the catalyst surface is provided as a pure transition metal oxide. 
     
     
         4 . The method of  claim 1 . wherein the catalyst surface comprises two or more transition metal oxides. 
     
     
         5 . The method of  claim 1 . wherein the method is carried out at a temperature in the range of about 0° C. to about 50° C. 
     
     
         6 . The method of  claim 1 . characterized in that the method is carried out at ambient pressure. 
     
     
         7 . The method of  claim 1 , characterized in that the method is carried out at a pressure in the range of about 1 atmospere to about 30 atmospheres. 
     
     
         8 . The method of  claim 1 . wherein the catalyst surface comprises at least one surface having a rutile structure. 
     
     
         9 . The method of  claim 1 . wherein the catalyst surface comprises at least one surface having a (110) facet. 
     
     
         10 . The method of  claim 1 . wherein an electrode potential that is less than about −0.5 V using a reversible hydrogen electrode (RHE) as a reference, is applied to the electrolytic cell. 
     
     
         11 . (canceled) 
     
     
         12 . The method of  claim 10 , wherein an electrode potential that is in the range of about −0.4 V to about −0.1 V is applied to the electrolytic cell. 
     
     
         13 . An electrochemical device for the reduction of carbon dioxide to methanol, or formic acid, comprising at least one electrochemical cell that comprises an anode and a cathode, wherein the cathode comprises at least one cathode electrode having at least one catalyst surface comprising at least one transition metal oxide selected from the group consisting of HfO 2 , OsO 2 , RhO 2 , CrO 2 , NbO 2 , MnO 2 , ZrO 2 , and VO 2 . 
     
     
         14 . The electrochemical device of  claim 13 , wherein the at least one transition metal oxide is selected from the group consisting of HfO 2 , NbO 2 , and ZrO 2 . 
     
     
         15 . The electrochemical device of  claim 13 , wherein the catalyst surface comprises at least one surface having a rutile structure. 
     
     
         16 . A process for the catalytic reduction of carbon dioxide, comprising:
 introducing CO 2  to a solution comprising at least one electrolyte in an electrolytic cell so that the CO 2  comes into contact with at least one cathode electrode surface; and   applying a potential to said electrolytic cell, whereby CO 2  reacts with protons to form methanol or formic acid;   wherein the cathode electrode surface comprises at least one catalyst surface comprising at least one transition metal oxide selected from the group consisting of HfO 2 , OSO 2 , RhO 2 , CrO 2 , NbO 2 , MnO 2 , ZrO 2 , and VO 2 .   
     
     
         17 . The process of  claim 16 , wherein the at least one transition metal oxide is selected from the group consisting of HfO 2 , NbO 2 , and ZrO 2 . 
     
     
         18 . The process of  claim 16 , wherein the process is carried out at a pressure in the range of about 1 to 20 atmospheres and a temperature in the range of about 0° C. to about 50° C. 
     
     
         19 . The process of  claim 16 , wherein the catalyst surface comprises at least one surface having a rutile structure. 
     
     
         20 . The process of  claim 16 , wherein the catalyst surface comprises at least one surface having a (110) facet. 
     
     
         21 . The process of  claim 16 , wherein the process is carried out at a temperature in the range of about 0° C. to about 50° C. 
     
     
         22 . The process of  claim 16 , wherein the process is carried out at a temperature in the range of about 10° C. to about 40° C. 
     
     
         23 . The process of  claim 16 , wherein the process is carried out at ambient pressure.