Photocatalytic solar energy conversion has drawn increasing attention,which holds great potential to deal with the energy crisis and environmental issues.As a typical semiconductor photocatalyst,graphite nitrogen carb...Photocatalytic solar energy conversion has drawn increasing attention,which holds great potential to deal with the energy crisis and environmental issues.As a typical semiconductor photocatalyst,graphite nitrogen carbon(g-C_(3)N_(4))has been widely utilized owing to its nontoxicity and easy preparation properties.However,pristine g-C_(3)N_(4) also faces the limitations of unsatisfactory light absorption,few active sites,and a rapid combination of photo-induced charge.To further optimize the photochemical catalytic performance of g-C_(3)N_(4),tremendous efforts were devoted to modifying g-C_(3)N_(4),including morphological regulation,element doping,and heterogeneous engineering.Some considerable progress has been achieved in g-C_(3)N_(4)-based photocatalytic hydrogen generation(PHE)from water splitting,photocatalytic carbon dioxide reduction(PCR),photocatalytic nitrogen reduction(PNR),photocatalytic removal of pollutants,and photocatalytic bacteria elimination.However,a frontier and comprehensive summary of g-C_(3)N_(4)-based photocatalysis is rarely reported.Herein,we provide an all-inclusive and updated investigation of the recent advances in modification methods of g-C_(3)N_(4) and photocatalytic reactions based on g-C_(3)N_(4) in the past five years.This conclusive remark may provide a new physical insight into the development of g-C_(3)N_(4)-based solar energy conversion.展开更多
Electrocatalytic reduction of nitrate pollutants to produce ammonia offers an effective approach to realizing the artificial nitrogen cycle and replacing the energyintensive Haber-Bosch process.Nitrite is an important...Electrocatalytic reduction of nitrate pollutants to produce ammonia offers an effective approach to realizing the artificial nitrogen cycle and replacing the energyintensive Haber-Bosch process.Nitrite is an important intermediate product in the reduction of nitrate to ammonia.Therefore,the mechanism of converting nitrite into ammonia warrants further investigation.Molecular cobalt catalysts are regarded as promising for nitrite reduction reactions(NO_(2)^(−)RR).However,designing and controlling the coordination environment of molecular catalysts is crucial for studying the mechanism of NO_(2)^(−)RR and catalyst design.Herein,we develop a molecular platform of cobalt porphyrin with three coordination microenvironments(Co-N_(3)X_(1),X=N,O,S).Electrochemical experiments demonstrate that cobalt porphyrin with O coordination(CoOTPP)exhibits the lowest onset potential and the highest activity for NO_(2)^(−)RR in ammonia production.Under neutral,nonbuffered conditions over a wide potential range(−1.0 to−1.5 V versus AgCl/Ag),the Faradaic efficiency of nearly 90%for ammonia was achieved and reached 94.5%at−1.4 V versus AgCl/Ag,with an ammonia yield of 6,498μgh^(−1)and a turnover number of 22,869 at−1.5V versus AgCl/Ag.In situ characterization and density functional theory calculations reveal that modulating the coordination environment alters the electron transfer mode of the cobalt active center and the charge redistribution caused by the break of the ligand field.Therefore,this results in enhanced electrochemical activity for NO_(2)^(−)RR in ammonia production.This study provides valuable guidance for designing adjustments to the coordination environment of molecular catalysts to enhance catalytic activity.展开更多
基金supported by Jilin youth growth science and technology plan project(No.20220508019RC)the“Interdisciplinary integration and innovation”project of Jilin University in 2021(No.JLUXKJC2021QZ06)+6 种基金the Natural Science Foundation of Jilin Province(No.SKL202302017)the National Natural Science Foundation of China(Nos.22279041,22301099,and 82302277)the National Key Research and Development Program of China(No.2022YFC2105800)the 111 Project(No.B17020)the Science and Technology Innovation Program of Hunan Province(No.2022RC1232)Provincial Natural Science Foundation of Hunan(Grant No.2023JJ40087)Research Foundation of Education Bureau of Hunan Province(No.22B0896).
文摘Photocatalytic solar energy conversion has drawn increasing attention,which holds great potential to deal with the energy crisis and environmental issues.As a typical semiconductor photocatalyst,graphite nitrogen carbon(g-C_(3)N_(4))has been widely utilized owing to its nontoxicity and easy preparation properties.However,pristine g-C_(3)N_(4) also faces the limitations of unsatisfactory light absorption,few active sites,and a rapid combination of photo-induced charge.To further optimize the photochemical catalytic performance of g-C_(3)N_(4),tremendous efforts were devoted to modifying g-C_(3)N_(4),including morphological regulation,element doping,and heterogeneous engineering.Some considerable progress has been achieved in g-C_(3)N_(4)-based photocatalytic hydrogen generation(PHE)from water splitting,photocatalytic carbon dioxide reduction(PCR),photocatalytic nitrogen reduction(PNR),photocatalytic removal of pollutants,and photocatalytic bacteria elimination.However,a frontier and comprehensive summary of g-C_(3)N_(4)-based photocatalysis is rarely reported.Herein,we provide an all-inclusive and updated investigation of the recent advances in modification methods of g-C_(3)N_(4) and photocatalytic reactions based on g-C_(3)N_(4) in the past five years.This conclusive remark may provide a new physical insight into the development of g-C_(3)N_(4)-based solar energy conversion.
基金National Key Research and Development Program of China,Grant/Award Number:2022YFC2105800National Natural Science Foundation of China,Grant/Award Numbers:21901084,21905106,22279041+2 种基金Higher Education Discipline Innovation Project,Grant/Award Number:B17020Specific Research Fund of the Innovation Platform for Academicians of Hainan Province,China,Grant/Award Number:YSPTZX202321Natural Science Foundation of Jilin Province,Grant/Award Number:SKL202302017.
文摘Electrocatalytic reduction of nitrate pollutants to produce ammonia offers an effective approach to realizing the artificial nitrogen cycle and replacing the energyintensive Haber-Bosch process.Nitrite is an important intermediate product in the reduction of nitrate to ammonia.Therefore,the mechanism of converting nitrite into ammonia warrants further investigation.Molecular cobalt catalysts are regarded as promising for nitrite reduction reactions(NO_(2)^(−)RR).However,designing and controlling the coordination environment of molecular catalysts is crucial for studying the mechanism of NO_(2)^(−)RR and catalyst design.Herein,we develop a molecular platform of cobalt porphyrin with three coordination microenvironments(Co-N_(3)X_(1),X=N,O,S).Electrochemical experiments demonstrate that cobalt porphyrin with O coordination(CoOTPP)exhibits the lowest onset potential and the highest activity for NO_(2)^(−)RR in ammonia production.Under neutral,nonbuffered conditions over a wide potential range(−1.0 to−1.5 V versus AgCl/Ag),the Faradaic efficiency of nearly 90%for ammonia was achieved and reached 94.5%at−1.4 V versus AgCl/Ag,with an ammonia yield of 6,498μgh^(−1)and a turnover number of 22,869 at−1.5V versus AgCl/Ag.In situ characterization and density functional theory calculations reveal that modulating the coordination environment alters the electron transfer mode of the cobalt active center and the charge redistribution caused by the break of the ligand field.Therefore,this results in enhanced electrochemical activity for NO_(2)^(−)RR in ammonia production.This study provides valuable guidance for designing adjustments to the coordination environment of molecular catalysts to enhance catalytic activity.
