Ca-type todorokite catalysts were designed and prepared by a simple redox method and applied to the selective reduction of NO_(x) by NH_(3)(NH_(3)-SCR)for the first time.Compared with the Na-type manjiroite prepared b...Ca-type todorokite catalysts were designed and prepared by a simple redox method and applied to the selective reduction of NO_(x) by NH_(3)(NH_(3)-SCR)for the first time.Compared with the Na-type manjiroite prepared by the same method,the todorokite catalysts with different Mn/Ca ratios showed greatly improved catalytic activity for NO_(x) reduction.Among them,Mn8Ca4 catalyst exhibited the best NH_(3)-SCR performance,achieving 90%NO_(x) conversion within temperature range of 70-275℃ and having a high sulphur resistance.Compared to the Na-type manjiroite sample,Ca-type todorokite catalysts possessed an increased size of tunnel,resulting in a larger specific surface area.As increased the amounts of Ca doping,the Na content in Ca-type todorokite catalysts significantly decreased,providing larger amounts of Bronsted acid sites for NH_(3) adsorption to produce NH_(4)^(+).The NH_(4)^(+)species were highly active for reaction with NO+O_(2),playing a determining role in NH_(3)-SCR process at low temperatures.Meanwhile,larger amounts of surface adsorbed oxygen contained over the Ca-doping samples than that over Na-type manjiroite,promoting the oxidation of NO and fast SCR processes.Over the Ca-type todorokite catalysts,furthermore,nitrates produced during the flow of NO+O_(2),were more active for reaction with NH_(3) than that over Na-type manjiroite,benefiting the occurrence of NH_(3)-SCR process.This study provides novel insights into the design of NH_(3)-SCR catalysts with high performance.展开更多
Na-type bentonite is commonly used as a tunnel backfilling material to prevent groundwater and radionuclide migration during the construction of a geological disposal system for high-level radioactive waste in Japan. ...Na-type bentonite is commonly used as a tunnel backfilling material to prevent groundwater and radionuclide migration during the construction of a geological disposal system for high-level radioactive waste in Japan. However, host rock fractures with strong water flow can develop groundwater paths in the backfilling material. Especially, the alteration to Ca-type bentonite causes degradation of the barrier performance and accelerates the development of groundwater paths. Additionally, using cementitious materials gradually changes pH between 13 and 8. High alkaline groundwater results in high solubility of silicic acid; therefore, silicic acid is eluted from the host rock. Downstream, in the low alkaline area, the groundwater becomes supersaturated in silicic acid. This acid is deposited on Ca-type bentonite, thus leading to the clogging of the groundwater paths. In the present study, we investigate the silicic acid deposition rate on Ca-type bentonite under 288-323 K for depths greater or equal to 500 m. The results indicate that temperature does not affect the silicic acid deposition rate up to 323 K. However, in this temperature range, the deposition of silicic acid on Ca-type bentonite in backfilled tunnels results in clogging of the flow paths.展开更多
基金supported by Self-deployed Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(No.E055C003)the National Natural Science Foundation of China(Nos.U20B6004 and 22072179)
文摘Ca-type todorokite catalysts were designed and prepared by a simple redox method and applied to the selective reduction of NO_(x) by NH_(3)(NH_(3)-SCR)for the first time.Compared with the Na-type manjiroite prepared by the same method,the todorokite catalysts with different Mn/Ca ratios showed greatly improved catalytic activity for NO_(x) reduction.Among them,Mn8Ca4 catalyst exhibited the best NH_(3)-SCR performance,achieving 90%NO_(x) conversion within temperature range of 70-275℃ and having a high sulphur resistance.Compared to the Na-type manjiroite sample,Ca-type todorokite catalysts possessed an increased size of tunnel,resulting in a larger specific surface area.As increased the amounts of Ca doping,the Na content in Ca-type todorokite catalysts significantly decreased,providing larger amounts of Bronsted acid sites for NH_(3) adsorption to produce NH_(4)^(+).The NH_(4)^(+)species were highly active for reaction with NO+O_(2),playing a determining role in NH_(3)-SCR process at low temperatures.Meanwhile,larger amounts of surface adsorbed oxygen contained over the Ca-doping samples than that over Na-type manjiroite,promoting the oxidation of NO and fast SCR processes.Over the Ca-type todorokite catalysts,furthermore,nitrates produced during the flow of NO+O_(2),were more active for reaction with NH_(3) than that over Na-type manjiroite,benefiting the occurrence of NH_(3)-SCR process.This study provides novel insights into the design of NH_(3)-SCR catalysts with high performance.
文摘Na-type bentonite is commonly used as a tunnel backfilling material to prevent groundwater and radionuclide migration during the construction of a geological disposal system for high-level radioactive waste in Japan. However, host rock fractures with strong water flow can develop groundwater paths in the backfilling material. Especially, the alteration to Ca-type bentonite causes degradation of the barrier performance and accelerates the development of groundwater paths. Additionally, using cementitious materials gradually changes pH between 13 and 8. High alkaline groundwater results in high solubility of silicic acid; therefore, silicic acid is eluted from the host rock. Downstream, in the low alkaline area, the groundwater becomes supersaturated in silicic acid. This acid is deposited on Ca-type bentonite, thus leading to the clogging of the groundwater paths. In the present study, we investigate the silicic acid deposition rate on Ca-type bentonite under 288-323 K for depths greater or equal to 500 m. The results indicate that temperature does not affect the silicic acid deposition rate up to 323 K. However, in this temperature range, the deposition of silicic acid on Ca-type bentonite in backfilled tunnels results in clogging of the flow paths.
