Metal compound based catalysts for electrosynthesis of hydrogen peroxide and linear paired electrochemical valorization of biomass-derived feedstocks

Abstract

Disclosed herein is an electrochemical cell comprising an electrolyte and a cathode immersed in the electrolyte, wherein the cathode comprises a two-electron oxygen reduction reaction (2e − ORR) electrocatalyst composed of a metal chalcogenide. Also disclosed are methods for production of hydrogen peroxide or preparing oxidation products of a biomass-derived feedstock with the electrochemical cells described herein.

1 . An electrochemical cell comprising an electrolyte and a cathode immersed in the electrolyte,
 wherein the cathode comprises a two-electron oxygen reduction reaction (2e −  ORR) electrocatalyst composed of a metal chalcogenide,   wherein the metal is Ni or Pd.   
     
     
         2 . The electrochemical cell of  claim 1 , wherein the metal chalcogenide comprises c-NiSe 2 . 
     
     
         3 . The electrochemical cell of  claim 1 , wherein the electrolyte has a pH below 4.0, optionally wherein the electrolyte has a pH between 0.0 and 4.0 pH or any pH therebetween. 
     
     
         4 . The electrochemical cell of  claim 1 , wherein the metal chalcogenide comprises layered PdSe 2 . 
     
     
         5 . The electrochemical cell of  claim 1 , wherein the electrolyte has a pH above 4.0, optionally wherein the electrolyte has a pH between 4.0 and 8.0 pH or any pH therebetween. 
     
     
         6 . The electrochemical cell of  claim 1 , wherein the electrolyte comprises oxygen (O 2 ), hydrogen peroxide (H 2 O 2 ), hydroxyl radical (·OH), a regenerable metal ion, and a first biomass-derived feedstock. 
     
     
         7 . The electrochemical cell of  claim 6  further comprising an acidic anolyte and an anode immersed in the anolyte, wherein the anolyte comprises a second biomass-derived feedstock. 
     
     
         8 . A method for production of hydrogen peroxide, the method comprising introducing oxygen into the electrochemical cell according to any one of  claim 1  under conditions sufficient for preparing the hydrogen peroxide. 
     
     
         9 . An electrochemical cell comprising an acidic catholyte, a cathode immersed in the catholyte, an acidic anolyte, and an anode immersed in the anolyte,
 wherein the cathode comprises a two-electron oxygen reduction reaction (2e −  ORR) electrocatalyst comprised of a metal chalcogenide and the catholyte comprises oxygen (O 2 ), hydrogen peroxide (H 2 O 2 ), hydroxyl radical (·OH), a regenerable metal ion, and a first biomass-derived feedstock, and wherein the anolyte comprises a second biomass-derived feedstock.   
     
     
         10 . The electrochemical cell of  claim 9 , wherein the two-electron oxygen reduction reaction (2e −  ORR) electrocatalyst comprises a metal chalcogenide. 
     
     
         11 . The electrochemical cell of  claim 10 , wherein the metal chalcogenide comprises an earth-abundant metal or a noble metal. 
     
     
         12 . The electrochemical cell of  claim 10 , wherein the metal chalcogenide comprises Ni, Co, Fe, Cu, Mn, Pd, or any combination thereof. 
     
     
         13 . The electrochemical cell of  claim 10 , wherein the metal chalcogenide comprises c-NiSe 2 , PdSe 2 , pyrite or marcasite type CoSe 2 , pyrite type CoS 2 , or CuCO 2-x Ni x S 4 . 
     
     
         14 . The electrochemical cell of  claim 9 , wherein the acidic catholyte and/or the acidic anolyte has a pH between 0.0 and 4.0 pH. 
     
     
         15 . The electrochemical cell of  claim 9 , wherein the regenerable metal ion is Fe 2+ . 
     
     
         16 . The electrochemical cell of  claim 9 , wherein each of the catholyte and the anolyte further comprise oxidation products of the first biomass-derived feed stock and the second biomass derived feed stock. 
     
     
         17 . A method for preparing an oxidation product of a biomass-derived feedstock, the method comprising introducing the biomass-derived feedstock into the electrochemical cell according to  claim 1  under conditions sufficient for preparing the oxidation product. 
     
     
         18 . The method of  claim 16 , wherein a potential between 0.00 and 0.70 V vs. RHE is applied to the cathode. 
     
     
         19 . A method for preparing an oxidation product of a biomass-derived feedstock, the method comprising introducing the biomass-derived feedstock into the electrochemical cell according to  claim 9  under conditions sufficient for preparing the oxidation product. 
     
     
         20 . The method of  claim 18 , wherein less than 1.0 V of externally applied bias is applied.