The Fenton-like process shows promising potential to generate reactive oxygen species for the reme-diation of increasingly environmental pollutants.However,the slow development of high-activity cata-lysts with strong ...The Fenton-like process shows promising potential to generate reactive oxygen species for the reme-diation of increasingly environmental pollutants.However,the slow development of high-activity cata-lysts with strong stability and low leaching of metal ions has greatly inhibited scale-up application of this technology.Here,cobalt(Co)/nitrogen(N)atom co-curved carbon nanorod(CoNC)containing highly uniform CoN_(x)active sites is developed as a Fenton-like catalyst for the effective catalytic oxidation of various organics via peroxymonosulfate(PMS)activation with high stability.As confirmed by the exper-imental results,singlet oxygen(^(1)O_(2))is the dominant active species for the degradation of the organ-ics,with a proportion of 100%.Furthermore,density functional theory calculations indicate that CoN_(2)C_(2)is the most effective ligand structure with more negative adsorption energy for PMS and the shortest length Co-O bond,while the most reasonable generation pathway for^(1)O_(2)was CoN_(2)C_(2)-PMS→CoN_(2)C_(2)-OH∗→2O∗→^(1)O_(2).Further studies demonstrate that the electron can be transferred from the highest occupied molecular orbitals of the organics to the lowest unoccupied molecular orbitals of the PMS via CoN_(2)C_(2)action.In addition,the CoNC presents strong resistance to inorganic ions and natural organic matter in the Fenton-like catalysis process.The presence of CoN_(2)C_(2)active centre can significantly shorten the migration distance of the^(1)O_(2)generated from PMS activation,which further enhances the Fenton-like catalytic activity in terms of mineralising various organic contaminants with high efficiency over a wide pH range.展开更多
基金This work was financially supported from the Key Program of National Natural Science Foundation of China(No.42030713)the National Natural Science Foundation of China(No.42007358)+4 种基金the Guangdong Basic and Applied Basic Research Foundation(Nos.2020A1515110518 and2021A1515110369)the Hongkong Schol-arship Program(No.XJ2020059)the China Postdoctoral Sci-ence Foundation(No.2019M663382)the Ministry of Science and Technology of China for State Key Research and Development Project(No.2016YFC0400702)the YoungInnovativeTalent Project of Guangdong Provincial Department of Education(No.2019GKQNCX056).The authors would like to thank Shiyanjia Lab(www.shiyanjia.com)for the GC-MS measurements.
文摘The Fenton-like process shows promising potential to generate reactive oxygen species for the reme-diation of increasingly environmental pollutants.However,the slow development of high-activity cata-lysts with strong stability and low leaching of metal ions has greatly inhibited scale-up application of this technology.Here,cobalt(Co)/nitrogen(N)atom co-curved carbon nanorod(CoNC)containing highly uniform CoN_(x)active sites is developed as a Fenton-like catalyst for the effective catalytic oxidation of various organics via peroxymonosulfate(PMS)activation with high stability.As confirmed by the exper-imental results,singlet oxygen(^(1)O_(2))is the dominant active species for the degradation of the organ-ics,with a proportion of 100%.Furthermore,density functional theory calculations indicate that CoN_(2)C_(2)is the most effective ligand structure with more negative adsorption energy for PMS and the shortest length Co-O bond,while the most reasonable generation pathway for^(1)O_(2)was CoN_(2)C_(2)-PMS→CoN_(2)C_(2)-OH∗→2O∗→^(1)O_(2).Further studies demonstrate that the electron can be transferred from the highest occupied molecular orbitals of the organics to the lowest unoccupied molecular orbitals of the PMS via CoN_(2)C_(2)action.In addition,the CoNC presents strong resistance to inorganic ions and natural organic matter in the Fenton-like catalysis process.The presence of CoN_(2)C_(2)active centre can significantly shorten the migration distance of the^(1)O_(2)generated from PMS activation,which further enhances the Fenton-like catalytic activity in terms of mineralising various organic contaminants with high efficiency over a wide pH range.
