Electrochemically treated silver nanocluster catalyst, manufacturing method thereof, gas diffusion electrode including same, zero-gap cell including same, and carbon dioxide conversion method or syngas production method by using same

Abstract

The present invention relates to a silver nanocluster catalyst for electrochemically treated carbon dioxide conversion, water reduction reactions, or syngas synthesis involving a mixture of hydrogen and carbon monoxide; a gas diffusion electrode comprising the same; a zero-gap reactor comprising the same; and a method for converting carbon dioxide using the same, which exhibits excellent conversion efficiency and high selectivity.

1 . A silver nanocluster catalyst represented by the following Chemical Formula 1:
   XAg 14 (R 1 ) n   [Chemical Formula 1]
   wherein R 1  is C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 3 -C 20  alkynyl, C 6 -C 20  aryl, C 3 -C 20  cycloalkyl, C 5 -C 20  heteroaryl, C 3 -C 20  heterocycloalkyl, C 6 -C 20  arylalkyl, or S—R 11 ;   R 11  is C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 3 -C 20  alkynyl, C 6 -C 20  aryl, C 3 -C 20  cycloalkyl, C 5 -C 20  heteroaryl, C 3 -C 20  heterocycloalkyl, or C 6 -C 20  arylalkyl;   X is a halogen; and   n is an integer from 6 to 11.   
     
     
         2 . The silver nanocluster catalyst according to  claim 1 ,
 wherein R 1  is C 1 -C 10  alkyl, C 2 -C 10  alkenyl, C 3 -C 10  alkynyl, C 6 -C 10  aryl, C 3 -C 10  cycloalkyl, C 5 -C 10  heteroaryl, C 3 -C 10  heterocycloalkyl, C 6 -C 10  arylalkyl, or S—R 11 ;   R 11  is C 1 -C 10  alkyl, C 2 -C 10  alkenyl, C 3 -C 10  alkynyl, C 6 -C 10  aryl, C 3 -C 10  cycloalkyl, C 5 -C 10  heteroaryl, C 3 -C 10  heterocycloalkyl, or C 6 -C 10  arylalkyl;   X is a halogen; and   n is an integer from 6 to 11.   
     
     
         3 . The silver nanocluster catalyst according to  claim 1 ,
 wherein R 1  is C 1 -C 10  alkyl, C 2 -C 10  alkenyl, C 3 -C 10  alkynyl, C 6 -C 10  aryl, or S—R 11 ;   R 11  is C 1 -C 10  alkyl, C 2 -C 10  alkenyl, C 3 -C 10  alkynyl, C 6 -C 10  aryl, or C 6 -C 10  arylalkyl;   X is a halogen; and   n is an integer from 6 to 11.   
     
     
         4 . The silver nanocluster catalyst according to  claim 1 ,
 wherein R 1  is C 1 -C 10  alkyl, C 2 -C 10  alkenyl, or C 3 -C 10  alkynyl;   X is a halogen; and   n is an integer from 6 to 11.   
     
     
         5 . The silver nanocluster catalyst according to  claim 1 ,
 wherein the silver nanocluster catalyst is used in a reaction selected from a carbon dioxide conversion reaction, a water reduction reaction, or a syngas synthesis reaction involving a mixture of hydrogen and carbon monoxide.   
     
     
         6 . A gas diffusion electrode comprising:
 a porous support and   the silver nanocluster catalyst according to  claim 1  fixed within the pores of the porous support.   
     
     
         7 . The gas diffusion electrode according to  claim 6 , wherein the porous support is made of carbon material. 
     
     
         8 . The gas diffusion electrode according to  claim 6 , wherein the average pore size of the porous support is 10 to 1000 nm. 
     
     
         9 . The gas diffusion electrode according to  claim 6 , wherein the average particle size of the silver nanoclusters is 1 to 5 nm. 
     
     
         10 . The gas diffusion electrode according to  claim 6 , wherein the silver nanocluster catalyst is supported at a density of 1 to 100 nmol/cm 2  of the porous support. 
     
     
         11 . A zero-gap reactor comprising:
 an anode;   a cathode containing the silver nanoclusters according to  claim 1 ; and   a separator positioned between the cathode and the anode.   
     
     
         12 . The zero-gap reactor according to  claim 10 , wherein the cathode is disposed in contact with one surface of the separator. 
     
     
         13 . The zero-gap reactor according to  claim 10 , wherein the anode is made of nickel, iron, or iridium, or a combination thereof. 
     
     
         14 . The zero-gap reactor according to  claim 10 , wherein the separator is an ion-exchange membrane. 
     
     
         15 . A method for converting carbon dioxide, the method comprising:
 supplying carbon dioxide to one surface of the cathode of a zero-gap reactor; and   obtaining carbon monoxide converted from carbon dioxide from the surface of the cathode, wherein the zero-gap reactor is according to  claim 11 .   
     
     
         16 . A method for producing a silver nanocluster catalyst represented by the following Chemical Formula 1, comprising:
 mixing a silver precursor, a ligand compound, an alkylammonium halide, and   a reducing agent; and electrochemically treating the mixture:
   XAg 14 (R 1 ) n   [Chemical Formula 1]
 
   wherein R 1  is C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 3 -C 20  alkynyl, C 6 -C 20  aryl, C 3 -C 20  cycloalkyl, C 5 -C 20  heteroaryl, C 3 -C 20  heterocycloalkyl, C 6 -C 20  arylalkyl, or S—R 11 ;   R 11  is C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 3 -C 20  alkynyl, C 6 -C 20  aryl, C 3 -C 20  cycloalkyl, C 5 -C 20  heteroaryl, C 3 -C 20  heterocycloalkyl, or C 6 -C 20  arylalkyl;   X is a halogen; and   n is an integer from 6 to 11.   
     
     
         17 . The method for producing a silver nanocluster catalyst according to  claim 15 , wherein the ligand compound is an alkyne compound of C 3 -C 20 . 
     
     
         18 . The method for producing a silver nanocluster catalyst according to  claim 15 , wherein the molar ratio of the silver precursor to the alkylammonium halide is 1:0.01 to 0.5. 
     
     
         19 . The method for producing a silver nanocluster catalyst according to  claim 16 , wherein the silver precursor is selected from AgNO 3 , AgBF 4 , AgCF 3 SO 3 , AgClO 4 , AgO 2 CCH 3 , and AgPF 6 . 
     
     
         20 . A method for producing a silver nanocluster catalyst represented by the following Chemical Formula 1, comprising:
 mixing a silver precursor, a ligand compound, and a halide compound in an aqueous solution; and   electrochemically treating the mixture:
   XAg 14 (R 1 ) n   [Chemical Formula 1]
 
   wherein R 1  is C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 3 -C 20  alkynyl, C 6 -C 20  aryl, C 3 -C 20  cycloalkyl, C 5 -C 20  heteroaryl, C 3 -C 20  heterocycloalkyl, C 6 -C 20  arylalkyl, or S—R 11 ;   R 11  is C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 3 -C 20  alkynyl, C 6 -C 20  aryl, C 3 -C 20  cycloalkyl, C 5 -C 20  heteroaryl, C 3 -C 20  heterocycloalkyl, or C 6 -C 20  arylalkyl;   X is a halogen; and   n is an integer from 6 to 11.   
     
     
         21 . The method for producing a silver nanocluster catalyst according to  claim 20 , wherein the ligand compound is an alkyne compound of C 3 -C 20 . 
     
     
         22 . The method for producing a silver nanocluster catalyst according to  claim 20 , wherein the halide compound is an alkali metal salt.