Sm-doped Fe_(2)O_(3)catalysts,with a homogeneous distribution of Sm in Fe_(2)O_(3)nanoparticles,were synthesized using a citric acid-assisted sol-gel method.Kinetic studies show that the reaction rate for NO_(x)reduct...Sm-doped Fe_(2)O_(3)catalysts,with a homogeneous distribution of Sm in Fe_(2)O_(3)nanoparticles,were synthesized using a citric acid-assisted sol-gel method.Kinetic studies show that the reaction rate for NO_(x)reduction using the optimal catalyst(0.06 mol%doping of Sm in Fe_(2)O_(3))was nearly 11 times higher than that for pure Fe_(2)O_(3),when calculated based on specific surface area.Furthermore,the Fe_(0.94)Sm_(0.06)O_(x)catalyst maintains>83%NO_(x)conversion for 168 h at a high space velocity in the presence of SO_(2)and H_(2)O at 250℃.A substantial amount of surface-adsorbed oxygen was generated on the surface of Fe_(0.94)Sm_(0.06)O_(x),which promoted NO oxidation and the subsequent fast reaction between NO_(x)and NH_(3).The adsorption and activation of NH_(3)was also enhanced by Sm doping.In addition,Sm doping facilitated the decomposition of NH_(4)HSO_(4)on the surface of Fe_(0.94)Sm_(0.06)O_(x),resulting in its high activity and stability in the presence of SO_(2)+H_(2)O.展开更多
The electrochemical reduction of CO2 to give CO in the presence of O2 would allow the direct valorization of flue gases from fossil fuel combustion and of CO2 captured from air. However, it is a challenging task becau...The electrochemical reduction of CO2 to give CO in the presence of O2 would allow the direct valorization of flue gases from fossil fuel combustion and of CO2 captured from air. However, it is a challenging task because O2 reduction is thermodynamically favored over that of CO2. 5% O2 in CO2 near catalyst surface is sufficient to completely inhibit the CO2 reduction reaction. Here we report an O2-tolerant catalytic CO2 reduction electrode inspired by part of the natural photosynthesis unit. The electrode comprises of heterogenized cobalt phthalocyanine molecules serving as the cathode catalyst with >95% Faradaic efficiency(FE) for CO2 reduction to CO coated with a polymer of intrinsic microporosity that works as a CO2-selective layer with a CO2/O2 selectivity of $20. Integrated into a flow electrolytic cell, the hybrid electrode operating with a CO2 feed gas containing 5% O2 exhibits a FECOof 75.9% with a total current density of 27.3 mA/cm^2 at a cell voltage of 3.1 V. A FECO of 49.7% can be retained when the O2 fraction increases to 20%. Stable operation for 18 h is demonstrated. The electrochemical performance and O2 tolerance can be further enhanced by introducing cyano and nitro substituents to the phthalocyanine ligand.展开更多
文摘Sm-doped Fe_(2)O_(3)catalysts,with a homogeneous distribution of Sm in Fe_(2)O_(3)nanoparticles,were synthesized using a citric acid-assisted sol-gel method.Kinetic studies show that the reaction rate for NO_(x)reduction using the optimal catalyst(0.06 mol%doping of Sm in Fe_(2)O_(3))was nearly 11 times higher than that for pure Fe_(2)O_(3),when calculated based on specific surface area.Furthermore,the Fe_(0.94)Sm_(0.06)O_(x)catalyst maintains>83%NO_(x)conversion for 168 h at a high space velocity in the presence of SO_(2)and H_(2)O at 250℃.A substantial amount of surface-adsorbed oxygen was generated on the surface of Fe_(0.94)Sm_(0.06)O_(x),which promoted NO oxidation and the subsequent fast reaction between NO_(x)and NH_(3).The adsorption and activation of NH_(3)was also enhanced by Sm doping.In addition,Sm doping facilitated the decomposition of NH_(4)HSO_(4)on the surface of Fe_(0.94)Sm_(0.06)O_(x),resulting in its high activity and stability in the presence of SO_(2)+H_(2)O.
基金supported by the U.S. National Science Foundation (CHE-1651717)the Croucher Fellowship for Postdoctoral Research+1 种基金supported by Global Innovation Initiative from Institute of International Educationsupport from Shenzhen Fundamental Research Funding (JCYJ20160608140827794)
文摘The electrochemical reduction of CO2 to give CO in the presence of O2 would allow the direct valorization of flue gases from fossil fuel combustion and of CO2 captured from air. However, it is a challenging task because O2 reduction is thermodynamically favored over that of CO2. 5% O2 in CO2 near catalyst surface is sufficient to completely inhibit the CO2 reduction reaction. Here we report an O2-tolerant catalytic CO2 reduction electrode inspired by part of the natural photosynthesis unit. The electrode comprises of heterogenized cobalt phthalocyanine molecules serving as the cathode catalyst with >95% Faradaic efficiency(FE) for CO2 reduction to CO coated with a polymer of intrinsic microporosity that works as a CO2-selective layer with a CO2/O2 selectivity of $20. Integrated into a flow electrolytic cell, the hybrid electrode operating with a CO2 feed gas containing 5% O2 exhibits a FECOof 75.9% with a total current density of 27.3 mA/cm^2 at a cell voltage of 3.1 V. A FECO of 49.7% can be retained when the O2 fraction increases to 20%. Stable operation for 18 h is demonstrated. The electrochemical performance and O2 tolerance can be further enhanced by introducing cyano and nitro substituents to the phthalocyanine ligand.
