Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)acc...Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.展开更多
Atlantic Meridional Overturning Circulation(AMOC)plays a central role in long-term climate variations through its heat and freshwater transports,which can collapse under a rapid increase of greenhouse gas forcing in c...Atlantic Meridional Overturning Circulation(AMOC)plays a central role in long-term climate variations through its heat and freshwater transports,which can collapse under a rapid increase of greenhouse gas forcing in climate models.Previous studies have suggested that the deviation of model parameters is one of the major factors in inducing inaccurate AMOC simulations.In this work,with a low-resolution earth system model,the authors try to explore whether a reasonable adjustment of the key model parameter can help to re-establish the AMOC after its collapse.Through a new optimization strategy,the extra freshwater flux(FWF)parameter is determined to be the dominant one affecting the AMOC’s variability.The traditional ensemble optimal interpolation(EnOI)data assimilation and new machine learning methods are adopted to optimize the FWF parameter in an abrupt 4×CO_(2) forcing experiment to improve the adaptability of model parameters and accelerate the recovery of AMOC.The results show that,under an abrupt 4×CO_(2) forcing in millennial simulations,the AMOC will first collapse and then re-establish by the default FWF parameter slowly.However,during the parameter adjustment process,the saltier and colder sea water over the North Atlantic region are the dominant factors in usefully improving the adaptability of the FWF parameter and accelerating the recovery of AMOC,according to their physical relationship with FWF on the interdecadal timescale.展开更多
The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developi...The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developing high oxide-ion conductivity in the electrolyte layer of SOFCs.In this context,for the first time,a dielectric material,CaCu_(3)Ti_(4)O_(12)(CCTO)is designed for LT-SOFCs electrolyte application in this study.Both individual CCTO and its heterostructure materials with a p-type Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2−δ)(NCAL)semiconductor are evaluated as alternative electrolytes in LT-SOFC at 450–550℃.The single cell with the individual CCTO electrolyte exhibits a power output of approximately 263 mW cm^(-2) and an open-circuit voltage(OCV)of 0.95 V at 550℃,while the cell with the CCTO–NCAL heterostructure electrolyte capably delivers an improved power output of approximately 605 mW cm^(-2) along with a higher OCV over 1.0 V,which indicates the introduction of high hole-conducting NCAL into the CCTO could enhance the cell performance rather than inducing any potential short-circuiting risk.It is found that these promising outcomes are due to the interplay of the dielectric material,its structure,and overall properties that led to improve electrochemical mechanism in CCTO–NCAL.Furthermore,density functional theory calculations provide the detailed information about the electronic and structural properties of the CCTO and NCAL and their heterostructure CCTO–NCAL.Our study thus provides a new approach for developing new advanced electrolytes for LT-SOFCs.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22479097)the Shanghai Science and Technology Committee(Grant No.23ZR1433000)the National High-Level Talent Program for Young Scholars,the Start-up Fund(F.S.)from Shanghai Jiao Tong University.
文摘Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.
基金supported by the National Key R&D Program of China [grant number 2023YFF0805202]the National Natural Science Foun-dation of China [grant number 42175045]the Strategic Priority Research Program of the Chinese Academy of Sciences [grant number XDB42000000]。
文摘Atlantic Meridional Overturning Circulation(AMOC)plays a central role in long-term climate variations through its heat and freshwater transports,which can collapse under a rapid increase of greenhouse gas forcing in climate models.Previous studies have suggested that the deviation of model parameters is one of the major factors in inducing inaccurate AMOC simulations.In this work,with a low-resolution earth system model,the authors try to explore whether a reasonable adjustment of the key model parameter can help to re-establish the AMOC after its collapse.Through a new optimization strategy,the extra freshwater flux(FWF)parameter is determined to be the dominant one affecting the AMOC’s variability.The traditional ensemble optimal interpolation(EnOI)data assimilation and new machine learning methods are adopted to optimize the FWF parameter in an abrupt 4×CO_(2) forcing experiment to improve the adaptability of model parameters and accelerate the recovery of AMOC.The results show that,under an abrupt 4×CO_(2) forcing in millennial simulations,the AMOC will first collapse and then re-establish by the default FWF parameter slowly.However,during the parameter adjustment process,the saltier and colder sea water over the North Atlantic region are the dominant factors in usefully improving the adaptability of the FWF parameter and accelerating the recovery of AMOC,according to their physical relationship with FWF on the interdecadal timescale.
基金National Natural Science Foundation of China(NSFC)supported this work under Grant No.32250410309,11674086,51736006,and 51772080funding from Science and Technology Department of Jiangsu Province under Grant No.BE2022029Shenzhen University under Grant No.86902/000248 also supported part of this work.
文摘The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developing high oxide-ion conductivity in the electrolyte layer of SOFCs.In this context,for the first time,a dielectric material,CaCu_(3)Ti_(4)O_(12)(CCTO)is designed for LT-SOFCs electrolyte application in this study.Both individual CCTO and its heterostructure materials with a p-type Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2−δ)(NCAL)semiconductor are evaluated as alternative electrolytes in LT-SOFC at 450–550℃.The single cell with the individual CCTO electrolyte exhibits a power output of approximately 263 mW cm^(-2) and an open-circuit voltage(OCV)of 0.95 V at 550℃,while the cell with the CCTO–NCAL heterostructure electrolyte capably delivers an improved power output of approximately 605 mW cm^(-2) along with a higher OCV over 1.0 V,which indicates the introduction of high hole-conducting NCAL into the CCTO could enhance the cell performance rather than inducing any potential short-circuiting risk.It is found that these promising outcomes are due to the interplay of the dielectric material,its structure,and overall properties that led to improve electrochemical mechanism in CCTO–NCAL.Furthermore,density functional theory calculations provide the detailed information about the electronic and structural properties of the CCTO and NCAL and their heterostructure CCTO–NCAL.Our study thus provides a new approach for developing new advanced electrolytes for LT-SOFCs.
