Method of electrochemically depositing high-activity electrocatalysts

Abstract

The method begins by forming a solution comprising catalyst precursors, electrolyte and a solvent. Electrodes are inserted into the solution comprising an anode electrode and a cathode electrode. Electrochemical deposition then occurs wherein a current is passed between the electrodes. In this method at least one additional step of: i) heating the solution prior to and during the electrochemical deposition; ii) increasing the concentration of the catalyst precursors in the solution to greater than 0.1 millimolar; iii) performing the electrochemical deposition by a pulsed current; and iv) adding chemical promoters to the solution.

1 . A method comprising:
 forming a solution comprising catalyst precursors, electrolyte and a solvent;   inserting electrodes comprising an anode electrode and a cathode electrode in the solution; and   performing electrochemical deposition by passing a current between the electrodes,   wherein the method includes at least one additional step of:   i) heating the solution prior to and during the electrochemical deposition;   ii) increasing the concentration of catalyst precursor in the solution to greater than 0.1 millimolar;   iii) performing the electrochemical deposition by a pulsed current; and   iv) adding a chemical promoter to the solution.   
     
     
         2 . The method of  claim 1 , wherein the catalyst precursor is selected from a metal, a metal salt, a metal alloy, an oxometallate compound, an organometallic reagent or any combination of the above. 
     
     
         3 . The method of  claim 1 , wherein the electrolyte is selected from any chemical compound capable of conducting electricity. 
     
     
         4 . The method of  claim 1 , wherein the solvent is selected from any chemical compound capable of dissolving the catalyst precursors and can enable the passage of electricity. 
     
     
         5 . The method of  claim 1 , wherein the solution is heated to a temperature above room temperature. 
     
     
         6 . The method of  claim 1 , wherein the solution is heated above 75° C. 
     
     
         7 . The method of  claim 1 , wherein the quantity of the catalyst precursor in the solution is greater than 0.1 millimolar. 
     
     
         8 . The method of  claim 1 , wherein the quantity of the catalyst precursor in the solution is greater than 100 millimolar. 
     
     
         9 . The method of  claim 1 , wherein the current is pulsed with an on:off time ratio in the range of 1:0.001 to 1:1000. 
     
     
         10 . The method of  claim 1 , wherein the current is pulsed with an on:off time ratio of 1:99. 
     
     
         11 . The method of  claim 1 , wherein the chemical promoter contains one or more of the following functional groups: sulfate, sulfonate, phosphate, carboxylate, alcohols, polyol, polyacids, amines, quaternary ammonium, paraquats and diquats. 
     
     
         12 . The method of  claim 1 , wherein at least two additional steps are performed. 
     
     
         13 . The method of  claim 1 , wherein at least three additional steps are performed. 
     
     
         14 . A method comprising:
 forming a solution comprising catalyst precursors, electrolyte and a solvent;   inserting electrodes comprising an anode electrode and a cathode electrode in the solution;   heating the solution to a temperature above room temperature; and   performing electrochemical deposition by passing a current between the electrodes.   
     
     
         15 . A method comprising:
 forming a solution comprising catalyst precursors, electrolyte and a solvent, wherein the quantity of the catalyst precursors in the solution is greater than 0.1 millimolar;   inserting electrodes comprising an anode electrode and a cathode electrode in the solution; and   performing electrochemical deposition by passing a current between the electrodes.   
     
     
         16 . A method comprising:
 forming a solution comprising catalyst precursors, electrolyte and a solvent;   inserting electrodes comprising an anode electrode and a cathode electrode in the solution; and   performing electrochemical deposition by passing a pulsed current between the electrodes.   
     
     
         17 . A method comprising:
 forming a solution comprising catalyst precursors, electrolyte, solvent and a chemical promoter;   inserting electrodes comprising an anode electrode and a cathode electrode in the solution; and   performing electrochemical deposition by passing a current between the electrodes.   
     
     
         18 . A method comprising:
 forming a solution comprising catalyst precursors, electrolyte, solvent and a chemical promoter, wherein the quantity of the catalyst precursors in the solution is greater than 0.1 millimolar;   inserting electrodes comprising an anode electrode and a cathode electrode in the solution;   heating the solution to a temperature above room temperature;   performing electrochemical deposition by passing a pulsed current between the electrodes to produce an enhanced anode electrode; and   performing electrolysis on an oxygenate solution using the enhanced electrodes both as an anode and a cathode.   
     
     
         19 . The method of  claim 18 , wherein the solution is heated above 75° C. 
     
     
         20 . The method of  claim 18 , wherein the quantity of the catalyst precursor in the solution is greater than 100 millimolar. 
     
     
         21 . The method of  claim 18 , wherein the current is pulsed with an on:off time ratio in the range of 1:0.001 to 1:1000. 
     
     
         22 . The method of  claim 18 , wherein the current is pulsed with an on:off time ratio of 1:99. 
     
     
         23 . The method of  claim 18 , wherein the chemical promoter contains one or more of the following functional groups: sulfate, sulfonate, phosphate, carboxylate, alcohols, polyol, polyacids, amines, quaternary ammonium, paraquats and diquats. 
     
     
         24 . A method comprising:
 forming a solution comprising catalyst precursors, electrolyte, solvent and a chemical promoter, wherein the quantity of the catalyst precursors in the solution is greater than 100 millimolar;   inserting electrodes comprising an anode electrode and a cathode electrode in the solution;   heating the solution to a temperature above 75° C.;   performing electrochemical deposition by passing a pulsed current between the electrodes, wherein the current is pulsed with an on:off time ratio of 1:99 to produce an enhanced anode and cathode; and   performing electrolysis on an oxygenate solution using the enhanced electrodes both as an anode and a cathode.