Oxygen Vacancy-Controlled CuOx/N,Se Co-Doped Porous Carbon via Plasma-Treatment for Enhanced Electro-Reduction of Nitrate to Green Ammonia.

The electrochemical nitrate reduction reaction (NO3RR) is of significance in regards of environmentally friendly issues and green ammonia production. However, relatively low performance with a competitive hydrogen evolution reaction (HER) is a challenge to overcome for the NO3RR. In this study, oxygen vacancy-controlled copper oxide (CuOx) catalysts through a plasma treatment are successfully prepared and supported on high surface area porous carbon that are co-doped with N, Se species for its enhanced electrochemical properties. The oxygen vacancy-increased CuOx catalyst supported on the N,Se co-doped porous carbon (CuOx-H/NSePC) exhibited the highest NO3RR performance with faradaic efficiency (FE) of 87.2% and yield of 7.9 mg cm-2 h-1 for the ammonia production, representing significant enhancements of FE and ammonia yield as compared to the un-doped or the oxygen vacancy-decreased catalysts. This high performance should be attributed to a significant increase in the catalytic active sites with facilitated energetics from strategies of doping the catalytic materials and weakening the N─O bonding strength for the adsorption of NO3 - ions on the modulated oxygen vacancies. This results show a promise that co-doping of heteroatoms and regulating of oxygen vacancies can be key factors for performance enhancement, suggesting new guidelines for effective catalyst design of NO3RR.

Electrochemical Reduction of CO2 to CO by N,S Dual-Doped Carbon Nanoweb Catalysts.

Converting CO2 into useful chemicals through an electrocatalytic process is an attractive solution to reduce CO2 in the atmosphere. However, the process suffers from high overpotential, low activity, or poor product selectivity. In this study, N,S dual-doped carbon nanoweb (NSCNW) materials were proposed as an efficient nonmetallic electrocatalyst for CO2 reduction. The NSCNW catalysts preferentially and rapidly converted CO2 into CO with a high Faradaic efficiency of 93.4 % and a partial current density of -5.93 mA cm-2 at a low overpotential of 490 mV. A small Tafel slope value (93 mV dec-1 ) was obtained, demonstrating a high rate for CO2 reduction. Moreover, the catalysts also exhibited a quite stable current-density profile during 20 h with a high CO Faradaic efficiency above 90 % throughout the electrolysis reaction. The high catalytic performance of the catalysts for CO2 reduction could be attributed to synergistic effects associated with the structural advantages of 3 D carbon nanoweb structures and effective S doping of the carbon materials with the highest ratio of thiophene-like S to oxidized S species.