Selective catalytic NH_(3)-to-N_(2) oxidation(NH_(3)-SCO)is highly promising for abating NH_(3) emissions slipped from stationary flue gas after-treatment devices.Its practical application,however,is limited by the no...Selective catalytic NH_(3)-to-N_(2) oxidation(NH_(3)-SCO)is highly promising for abating NH_(3) emissions slipped from stationary flue gas after-treatment devices.Its practical application,however,is limited by the non-availability of low-cost catalysts with high activity and N_(2) selectivity.Here,using defect-rich nitrogen-doped carbon nanotubes(NCNT-AW)as the support,we developed a highly active and durable copper-based NH_(3)-SCO catalyst with a high abundance of cuprous(Cu^(+))sites.The obtained Cu/NCNT-AW catalyst demonstrated outstanding activity with a T_(50)(i.e.the temperature to reach 50% NH_(3) conversion)of 174℃ in the NH_(3)-SCO reaction,which outperformed not only the Cu catalyst supported on N-free O-functionalized CNTs(OCNTs)or NCNT with less surface defects,but also those most active Cu catalysts in open literature.Reaction kinetics measurements and temperature-programmed surface reactions using NH_(3)as a probe molecule revealed that the NH_(3)-SCO reaction on Cu/NCNT-AW follows an internal selective catalytic reaction(i-SCR)route involving nitric oxide(NO)as a key intermediate.According to mechanistic investigations by X-ray photoelectron spectroscopy,Raman spectroscopy,and X-ray absorption spectroscopy,the superior NH_(3)-SCO performance of Cu/NCNT-AW originated from a synergy of surface defects and N-dopants.Specifically,surface defects promoted the anchoring of Cu O nanoparticles on N-containing sites and,thereby,enabled efficient electron transfer from N to Cu O,increasing significantly the fraction of SCR-active Cu^(+)sites in the catalyst.This study puts forward a new idea for manipulating and utilizing the interplay of defects and N-dopants on carbon surfaces to fabricate Cu^(+)-rich Cu catalysts for efficient abatement of slip NH_(3)emissions via selective oxidation.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21806039,21976058)the Natural Science Foundation of Guangdong Province(No.2023A1515011682)+2 种基金the Fundamental Research Funds for the Central Universities(No.2022ZYGXZR018)the Science and Technology Program of Guangzhou(No.202102080490).P.C.appreciates the funding from the Pearl River Talent Recruitment Program of Guangdong Province(No.2019QN01L170)the Innovation&Entrepreneurship Talent Program of Shaoguan City。
文摘Selective catalytic NH_(3)-to-N_(2) oxidation(NH_(3)-SCO)is highly promising for abating NH_(3) emissions slipped from stationary flue gas after-treatment devices.Its practical application,however,is limited by the non-availability of low-cost catalysts with high activity and N_(2) selectivity.Here,using defect-rich nitrogen-doped carbon nanotubes(NCNT-AW)as the support,we developed a highly active and durable copper-based NH_(3)-SCO catalyst with a high abundance of cuprous(Cu^(+))sites.The obtained Cu/NCNT-AW catalyst demonstrated outstanding activity with a T_(50)(i.e.the temperature to reach 50% NH_(3) conversion)of 174℃ in the NH_(3)-SCO reaction,which outperformed not only the Cu catalyst supported on N-free O-functionalized CNTs(OCNTs)or NCNT with less surface defects,but also those most active Cu catalysts in open literature.Reaction kinetics measurements and temperature-programmed surface reactions using NH_(3)as a probe molecule revealed that the NH_(3)-SCO reaction on Cu/NCNT-AW follows an internal selective catalytic reaction(i-SCR)route involving nitric oxide(NO)as a key intermediate.According to mechanistic investigations by X-ray photoelectron spectroscopy,Raman spectroscopy,and X-ray absorption spectroscopy,the superior NH_(3)-SCO performance of Cu/NCNT-AW originated from a synergy of surface defects and N-dopants.Specifically,surface defects promoted the anchoring of Cu O nanoparticles on N-containing sites and,thereby,enabled efficient electron transfer from N to Cu O,increasing significantly the fraction of SCR-active Cu^(+)sites in the catalyst.This study puts forward a new idea for manipulating and utilizing the interplay of defects and N-dopants on carbon surfaces to fabricate Cu^(+)-rich Cu catalysts for efficient abatement of slip NH_(3)emissions via selective oxidation.
