Developing energy-efficient nitrite-to-ammonia(NO_(2)RR)conversion technologies while simultaneously enabling the electrochemical upcycling of waste polyethylene terephthalate(PET)plastics into highvalue-added chemica...Developing energy-efficient nitrite-to-ammonia(NO_(2)RR)conversion technologies while simultaneously enabling the electrochemical upcycling of waste polyethylene terephthalate(PET)plastics into highvalue-added chemicals is of great significance.Herein,an atomic oxygen vacancy(V_(o))engineering is developed to optimize the catalytic performance of V_(o2)-Co(OH)F nanoarray towards the NO_(2)RR and PET-derived ethylene glycol oxidation reaction(EGOR).The optimal V_(o2)-Co(OH)F achieves an ultralow operating potential of -0.03 V vs.RHE at -100 mA cm^(-2)and a remarkable NH_(3)Faradaic efficiency(FE)of 98.4% at -0.2 V vs.RHE for NO_(2)RR,and a high formate FE of 98.03% for EGOR.Operando spectroscopic analysis and theoretical calculations revealed that oxygen vacancies play a crucial role in optimizing the electronic structure of V_(o2)-Co(OH)F,modulating the adsorption free energies of key reaction intermediates,and lowering the reaction energy barrier,thereby enhancing its overall catalytic performance.Remarkably,the V_(o2)-Co(OH)F-based NO_(2)RR||EGOR electrolyzer realized high NH_(3)and formate yield rates of 33.9 and 44.9 mg h^(-1)cm^(-2)at 1.7 V,respectively,while demonstrating outstanding long-term stability over 100 h.This work provides valuable insights into the rational design of advanced electrocatalysts for co-electrolysis systems.展开更多
The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development ...The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development of efficient bifunctional electrocatalysts.Herein,we put forward a high-efficiency coelectrolysis system by coupling the nitrite reduction reaction(NO_(2)RR)and the glycerol oxidation reaction(GOR)over a novel heterogeneous β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl catalyst.Theβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl shows excellent bifunctional performance with high Faradaic efficiencies of formate(90.1%)and NH_(3)(91.9%)at cell voltage of 1.5 V,high yield rate of formate(89.6 mg h^(-1)cm^(-2))and NH_(3)(36.07 mg h^(-1)cm^(-2))at cell voltage of 1.9 V,and superior stability in an anion exchange membrane co-electrolyzer.The in-situ Raman result confirms the unique Co/Cu-based bimetallic synergistic sites of β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl towards superior GOR performance,while the operando Fourier transform infrared spectroscopy demonstrates the improved protonation kinetics of key intermediates and optimized water dissociation ability ofβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl for high NO_(2)RR activity.Our work illuminates alternative avenues to exploit the innovative and energy-saving technology for the co-production of high-added chemicals.展开更多
基金financially supported by the National Natural Science Foundation of China(22205205)the Fundamental Research Funds of Zhejiang Sci-Tech University(ZSTU,25262157Y)the staff of beamline BL11B and BL13SSW at Shanghai Synchrotron Radiation Facility for experimental support。
文摘Developing energy-efficient nitrite-to-ammonia(NO_(2)RR)conversion technologies while simultaneously enabling the electrochemical upcycling of waste polyethylene terephthalate(PET)plastics into highvalue-added chemicals is of great significance.Herein,an atomic oxygen vacancy(V_(o))engineering is developed to optimize the catalytic performance of V_(o2)-Co(OH)F nanoarray towards the NO_(2)RR and PET-derived ethylene glycol oxidation reaction(EGOR).The optimal V_(o2)-Co(OH)F achieves an ultralow operating potential of -0.03 V vs.RHE at -100 mA cm^(-2)and a remarkable NH_(3)Faradaic efficiency(FE)of 98.4% at -0.2 V vs.RHE for NO_(2)RR,and a high formate FE of 98.03% for EGOR.Operando spectroscopic analysis and theoretical calculations revealed that oxygen vacancies play a crucial role in optimizing the electronic structure of V_(o2)-Co(OH)F,modulating the adsorption free energies of key reaction intermediates,and lowering the reaction energy barrier,thereby enhancing its overall catalytic performance.Remarkably,the V_(o2)-Co(OH)F-based NO_(2)RR||EGOR electrolyzer realized high NH_(3)and formate yield rates of 33.9 and 44.9 mg h^(-1)cm^(-2)at 1.7 V,respectively,while demonstrating outstanding long-term stability over 100 h.This work provides valuable insights into the rational design of advanced electrocatalysts for co-electrolysis systems.
基金financially supported by the National Natural Science Foundation of China(22205205)the Science Foundation of Zhejiang Sci-Tech University(ZSTU)under Grant No.21062337-Y。
文摘The electrochemical biomass valorization of industrial by-products or pollutants using renewable electricity offers significant promise for carbon neutrality.However,the huge challenges still exist in the development of efficient bifunctional electrocatalysts.Herein,we put forward a high-efficiency coelectrolysis system by coupling the nitrite reduction reaction(NO_(2)RR)and the glycerol oxidation reaction(GOR)over a novel heterogeneous β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl catalyst.Theβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl shows excellent bifunctional performance with high Faradaic efficiencies of formate(90.1%)and NH_(3)(91.9%)at cell voltage of 1.5 V,high yield rate of formate(89.6 mg h^(-1)cm^(-2))and NH_(3)(36.07 mg h^(-1)cm^(-2))at cell voltage of 1.9 V,and superior stability in an anion exchange membrane co-electrolyzer.The in-situ Raman result confirms the unique Co/Cu-based bimetallic synergistic sites of β-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl towards superior GOR performance,while the operando Fourier transform infrared spectroscopy demonstrates the improved protonation kinetics of key intermediates and optimized water dissociation ability ofβ-Co(OH)_(2)/Cu_(2)(OH)_(3)Cl for high NO_(2)RR activity.Our work illuminates alternative avenues to exploit the innovative and energy-saving technology for the co-production of high-added chemicals.
