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
CsPbI_(2)Br perovskite solar cell has been extensively studied due to its exceptional thermal stability and relatively stable perovskite phase structure.However,the presence of bromine leads to a rapid crystallization...CsPbI_(2)Br perovskite solar cell has been extensively studied due to its exceptional thermal stability and relatively stable perovskite phase structure.However,the presence of bromine leads to a rapid crystallization rate of CsPbI_(2)Br films,resulting in small grain size and high defect density.Additionally,CsPbI_(2)Br demonstrates poor light absorption due to its wide bandgap.Therefore,it is crucial to control the crystallization rate and increase the film thickness to reduce defect density,enhance light absorption,and improve photovoltaic performance.In this study,we utilized a PbAc_(2)-incorporated twice spincoating(PTS) process to address these issues.Initially,PbAc_(2) was added to the CsPbI_(2)Br precursor solution to form a CsPbI_(2)Br film,which was then coated with the CsPbI_(2)Br precursor solution to produce the PTS film,Ac^(-)can delay the perovskite crystallization,leading to the formation of thicker and denser CsPbI_(2)Br films.Moreover,lone-pair electrons of the oxygen atom provided by Ac^(-)formed coordination bonds with under-coordinated Pb~(2+) ions to fill halogen ion vacancies,thereby reducing the defect density.Ultimately,the PTS CsPbI_(2)Br device achieved a peak power conversion efficiency(PCE) of 16.19% and maintained 96.7% of its initial PCE over 1500 h at room temperature under 25% relative humidity without any encapsulation.展开更多
Offshore carbon dioxide(CO_(2)) geological storage(OCGS) represents a significant strategy for addressing climate change by curtailing greenhouse gas emissions. Nonetheless, the risk of CO_(2) leakage poses a substant...Offshore carbon dioxide(CO_(2)) geological storage(OCGS) represents a significant strategy for addressing climate change by curtailing greenhouse gas emissions. Nonetheless, the risk of CO_(2) leakage poses a substantial concern associated with this technology. This study introduces an innovative approach for establishing OCGS leakage scenarios, involving four pivotal stages, namely, interactive matrix establishment, risk matrix evaluation, cause–effect analysis, and scenario development, which has been implemented in the Pearl River Estuary Basin in China. The initial phase encompassed the establishment of an interaction matrix for OCGS systems based on features, events, and processes. Subsequent risk matrix evaluation and cause–effect analysis identified key system components, specifically CO_(2) injection and faults/features. Building upon this analysis, two leakage risk scenarios were successfully developed, accompanied by the corresponding mitigation measures. In addition, this study introduces the application of scenario development to risk assessment, including scenario numerical simulation and quantitative assessment. Overall, this research positively contributes to the sustainable development and safe operation of OCGS projects and holds potential for further refinement and broader application to diverse geographical environments and project requirements. This comprehensive study provides valuable insights into the establishment of OCGS leakage scenarios and demonstrates their practical application to risk assessment, laying the foundation for promoting the sustainable development and safe operation of ocean CO_(2) geological storage projects while proposing possibilities for future improvements and broader applications to different contexts.展开更多
Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-speciality grout. Dicalcium silicate （Ca2SiO4） is the primary constituent ...Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-speciality grout. Dicalcium silicate （Ca2SiO4） is the primary constituent of a number of different types of cement. The β-Ca2SiO4 phase is metastable at room temperature and will transform into β-Ca2SiO4 at 663K. In this work, Portland cement is annealed at a temperature of 950K under pressures in the range of 0-5.5 CPa. The high pressure experiments are carried out in an apparatus with six anvil tops. The effect of high pressure on the obtaining nano-size β-Ca2SiO4 （C2S） process is investigated by x-ray diffraction and transmission electron microscopy. Experimental results show that the grain size of the C2S decreases with the increase of pressure. The volume fraction of the C2S phase increases with the pressure as the pressure is below 3 CPa, and then decreases （P 〉 3 GPa）. The nano-effect is very important to the stabilization of β-Ca2SiO4. The mechanism for the effects of the high pressure on the annealing process of the Portland cement is also discussed.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 Natural Science Foundation of China (U22A20142)the Fundamental Research Funds for the Central Universities (2023JC007)。
文摘CsPbI_(2)Br perovskite solar cell has been extensively studied due to its exceptional thermal stability and relatively stable perovskite phase structure.However,the presence of bromine leads to a rapid crystallization rate of CsPbI_(2)Br films,resulting in small grain size and high defect density.Additionally,CsPbI_(2)Br demonstrates poor light absorption due to its wide bandgap.Therefore,it is crucial to control the crystallization rate and increase the film thickness to reduce defect density,enhance light absorption,and improve photovoltaic performance.In this study,we utilized a PbAc_(2)-incorporated twice spincoating(PTS) process to address these issues.Initially,PbAc_(2) was added to the CsPbI_(2)Br precursor solution to form a CsPbI_(2)Br film,which was then coated with the CsPbI_(2)Br precursor solution to produce the PTS film,Ac^(-)can delay the perovskite crystallization,leading to the formation of thicker and denser CsPbI_(2)Br films.Moreover,lone-pair electrons of the oxygen atom provided by Ac^(-)formed coordination bonds with under-coordinated Pb~(2+) ions to fill halogen ion vacancies,thereby reducing the defect density.Ultimately,the PTS CsPbI_(2)Br device achieved a peak power conversion efficiency(PCE) of 16.19% and maintained 96.7% of its initial PCE over 1500 h at room temperature under 25% relative humidity without any encapsulation.
文摘Offshore carbon dioxide(CO_(2)) geological storage(OCGS) represents a significant strategy for addressing climate change by curtailing greenhouse gas emissions. Nonetheless, the risk of CO_(2) leakage poses a substantial concern associated with this technology. This study introduces an innovative approach for establishing OCGS leakage scenarios, involving four pivotal stages, namely, interactive matrix establishment, risk matrix evaluation, cause–effect analysis, and scenario development, which has been implemented in the Pearl River Estuary Basin in China. The initial phase encompassed the establishment of an interaction matrix for OCGS systems based on features, events, and processes. Subsequent risk matrix evaluation and cause–effect analysis identified key system components, specifically CO_(2) injection and faults/features. Building upon this analysis, two leakage risk scenarios were successfully developed, accompanied by the corresponding mitigation measures. In addition, this study introduces the application of scenario development to risk assessment, including scenario numerical simulation and quantitative assessment. Overall, this research positively contributes to the sustainable development and safe operation of OCGS projects and holds potential for further refinement and broader application to diverse geographical environments and project requirements. This comprehensive study provides valuable insights into the establishment of OCGS leakage scenarios and demonstrates their practical application to risk assessment, laying the foundation for promoting the sustainable development and safe operation of ocean CO_(2) geological storage projects while proposing possibilities for future improvements and broader applications to different contexts.
基金Supported by the National Natural Science Foundation of China under Grant No 11674274
文摘Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-speciality grout. Dicalcium silicate （Ca2SiO4） is the primary constituent of a number of different types of cement. The β-Ca2SiO4 phase is metastable at room temperature and will transform into β-Ca2SiO4 at 663K. In this work, Portland cement is annealed at a temperature of 950K under pressures in the range of 0-5.5 CPa. The high pressure experiments are carried out in an apparatus with six anvil tops. The effect of high pressure on the obtaining nano-size β-Ca2SiO4 （C2S） process is investigated by x-ray diffraction and transmission electron microscopy. Experimental results show that the grain size of the C2S decreases with the increase of pressure. The volume fraction of the C2S phase increases with the pressure as the pressure is below 3 CPa, and then decreases （P 〉 3 GPa）. The nano-effect is very important to the stabilization of β-Ca2SiO4. The mechanism for the effects of the high pressure on the annealing process of the Portland cement is also discussed.
