Catalytic conversion of nitrate(NO_(3)^(-))pollutants into ammonia(NH_(3))offers a sustainable and promising route for both wastewater treatment and NH_(3)synthesis.Alkali cations are prevalent in nitrate solutions,bu...Catalytic conversion of nitrate(NO_(3)^(-))pollutants into ammonia(NH_(3))offers a sustainable and promising route for both wastewater treatment and NH_(3)synthesis.Alkali cations are prevalent in nitrate solutions,but their roles beyond charge balance in catalytic NO_(3)^(-)conversion have been generally ignored.Herein,we report the promotion effect of K^(+)cations in KNO_(3)solution for NO_(3)^(-)reduction over a TiO_(2)-supported Ni single-atom catalyst(Ni_(1)/TiO_(2)).For photocatalytic NO_(3)^(-)reduction reaction,Ni_(1)/TiO_(2)exhibited a 1.9-fold NH_(3)yield rate with nearly 100%selectivity in KNO_(3)solution relative to that in NaNO_(3)solution.Mechanistic studies reveal that the K^(+)cations from KNO_(3)gradually bonded with the surface of Ni_(1)/TiO_(2),in situ forming a K-O-Ni moiety during reaction,whereas the Na^(+)ions were unable to interact with the catalyst in NaNO_(3)solution.The charge accumulation on the Ni sites induced by the incorporation of K atom promoted the adsorption and activation of NO_(3)^(-).Furthermore,the K-O-Ni moiety facilitated the multiple proton-electron coupling of NO_(3)^(-)into NH_(3)by stabilizing the intermediates.展开更多
基金financial support by the National Natural Science Foundation of China(12222508,U1932213,and 22308346)the Fundamental Research Funds for the Central Universities(WK2060000016)+5 种基金the USTC Research Funds of the Double First-Class Initiative(YD2310002005 and YD9990002014)the National Key R&D Program of China(2023YFA1506304)the Youth Innovation Promotion Association CAS(2020454)Xiaomi Young Talents ProgramJoint Funds from the Hefei National Synchrotron Radiation Laboratory(KY9990000202)Natural Science Foundation of Anhui Province(2208085QB42)。
文摘Catalytic conversion of nitrate(NO_(3)^(-))pollutants into ammonia(NH_(3))offers a sustainable and promising route for both wastewater treatment and NH_(3)synthesis.Alkali cations are prevalent in nitrate solutions,but their roles beyond charge balance in catalytic NO_(3)^(-)conversion have been generally ignored.Herein,we report the promotion effect of K^(+)cations in KNO_(3)solution for NO_(3)^(-)reduction over a TiO_(2)-supported Ni single-atom catalyst(Ni_(1)/TiO_(2)).For photocatalytic NO_(3)^(-)reduction reaction,Ni_(1)/TiO_(2)exhibited a 1.9-fold NH_(3)yield rate with nearly 100%selectivity in KNO_(3)solution relative to that in NaNO_(3)solution.Mechanistic studies reveal that the K^(+)cations from KNO_(3)gradually bonded with the surface of Ni_(1)/TiO_(2),in situ forming a K-O-Ni moiety during reaction,whereas the Na^(+)ions were unable to interact with the catalyst in NaNO_(3)solution.The charge accumulation on the Ni sites induced by the incorporation of K atom promoted the adsorption and activation of NO_(3)^(-).Furthermore,the K-O-Ni moiety facilitated the multiple proton-electron coupling of NO_(3)^(-)into NH_(3)by stabilizing the intermediates.
基金financially supported in part by the National Key R&D Program of China (2020YFA0406103)the National Natural Science Foundation of China (21725102, 22122506, 91961106, 22075267, 22109148)+4 种基金Strategic Priority Research Program of the Chinese Academy of Sciences (XDPB14)the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2019444)the Hundred Talents Program of the Chinese Academy of SciencesFundamental Research Funds for the Central Universities (WK2060000039)support from the USTC Center for Micro- and Nanoscale Research and Fabrication。
