The key to designing photocatalysts is to orient the migration of photogenerated electrons to the target active sites rather than dissipate at inert sites.Herein,we demonstrate that the doping of phosphorus(P)signific...The key to designing photocatalysts is to orient the migration of photogenerated electrons to the target active sites rather than dissipate at inert sites.Herein,we demonstrate that the doping of phosphorus(P)significantly enriches photogenerated electrons at Ni active sites and enhances the performance for CO_(2) reduction into syngas.During photocatalytic CO_(2) reduction,Ni single‐atom‐anchored P‐modulated carbon nitride showed an impressive syngas yield rate of 85μmol gcat^(−1)h^(−1) and continuously adjustable CO/H_(2) ratios ranging from 5:1 to 1:2,which exceeded those of most of the reported carbon nitride‐based single‐atom catalysts.Mechanistic studies reveal that P doping improves the conductivity of catalysts,which promotes photogenerated electron transfer to the Ni active sites rather than dissipate randomly at low‐activity nonmetallic sites,facilitating the CO_(2)‐to‐syngas photoreduction process.展开更多
Highly-efficient oxidation of 5-hydroxymethylfurtural(HMF) to 2,5-furandicarboxylic acid(FDCA) at low temperature with air as the oxidant is still challenging.Herein,inspired by the respirato ry electron transport cha...Highly-efficient oxidation of 5-hydroxymethylfurtural(HMF) to 2,5-furandicarboxylic acid(FDCA) at low temperature with air as the oxidant is still challenging.Herein,inspired by the respirato ry electron transport chain(ETC) of living cells mediated by electron carriers,we constructed artificial ETCs and transformed liquid flow fuel cells(LFFCs) to flexible reactors for efficient oxidation of HMF to produce FDCA under mild conditions.This LFFC reactor employed an electrodeposition modified nickel foam as an anode to promote HMF oxidation and(VO_(2))_(2)SO_(4) as a cathode electron carrier to facilitate the electron transfer to air.The reaction rate could be easily controlled by selecting the anode catalyst,adjusting the external loading and changing the cathodic electron carrier or oxidants.A maximal power density of 44.9 mW cm^(-2) at room temperature was achieved,while for FDCA production,short-circuit condition was preferred to achieve quick transfer of electrons.For a single batch operation with 0.1 M initial HMF,FDCA yield reached 97.1%.By fed-batch operation,FDCA concentration reached 144.5 g L^(-1) with a total yield of 96%.Ni^(2+)/Ni^(3+) redox couple was the active species mediating the electron transfer,while both experimental and DFT calculation results indicated that HMFCA pathway was the preferred reaction mechanism.展开更多
Offset-tracking is an essential method for deriving glacier flow rates using optical imagery.Sentinel-2(S2)and Landsat-8/9(L8/9)are popular optical satellites or constellations for polar studies,offering high spatial ...Offset-tracking is an essential method for deriving glacier flow rates using optical imagery.Sentinel-2(S2)and Landsat-8/9(L8/9)are popular optical satellites or constellations for polar studies,offering high spatial resolution with relatively short revisit time,wide swath width,and free accessibility.To evaluate and compare the precision of offset-tracking results yielded with these two kinds of data,in this study S2 and L8/9 imagery observed in Petermann Glacier in Greenland,Karakoram in High-Mountains Asia,and Amery Ice Shelf in the Antarctic are analyzed.Outliers and various systematic error sources in the offset-tracking results including orbital and strip errors were analyzed and eliminated at the pre-process stage.Precision at the off-glacier(bare rock)region was evaluated by presuming that no deformation occurred;then for both glacierized and the off-glacier regions,precision of velocity time series was evaluated based on error propagation theory.The least squares method based on connected components was used to solve flow rates time series based on multi-pair images offset-tracking.The results indicated that S2 achieved slightly higher precision than L8/9 in terms of both single-pair derived displacements and least square solved daily flow rates time series.Generally,the RMSE of daily velocity is 26%lower for S2 than L8/9.Moreover,S2 provided higher temporal resolution for monitoring glacier flow rates.展开更多
Dilatancy-controlled gas flow in preferential pathways plays a key role in the safety analysis of radioactive waste repositories.This is particularly the case for bentonite,an often-preferred barrier material.Gas flow...Dilatancy-controlled gas flow in preferential pathways plays a key role in the safety analysis of radioactive waste repositories.This is particularly the case for bentonite,an often-preferred barrier material.Gas flow in preferential pathways is characterized by localization and spontaneous behavior,which is challenging to simulate in numerical models due to strong hydro-mechanical coupling.To analyze a laboratory experiment in the framework of the DECOVALEX-2023 project,this study introduced a new approach of combining continuous modelling methods with spatial material properties derived from material heterogeneities and experimental observations.The proposed model utilized hydro-mechanical spatial distributions,namely Young’s modulus and gas entry pressure,and elastoplasticity combined with a linear swelling model.A conceptual strain-dependent permeability approach simulated dilatancycontrolled gas flow based on hydro-mechanical coupling.To test the effectiveness of the presented approach,a gas injection test in a compacted,saturated bentonite sample was simulated using the opensource code OpenGeoSys 5.8 and compared with experimental observations.The presented methodology is capable of simulating localized gas flow in preferential pathways.The spatial distributions of Young’s modulus and gas entry pressure affect the swelling pressure,relative permeability and,in combination with the strain-dependent permeability model,also the intrinsic permeability.展开更多
水气分散体系驱油技术是针对低渗透油田采出程度低研发的新型提高采收率技术,目前已在长庆油田取得明显增油效果,但分散体系中微气泡与孔隙作用复杂,对其微观驱油机理的研究正逐步深入。根据低渗透、非均质岩心的特点,制作边长为1.5 cm...水气分散体系驱油技术是针对低渗透油田采出程度低研发的新型提高采收率技术,目前已在长庆油田取得明显增油效果,但分散体系中微气泡与孔隙作用复杂,对其微观驱油机理的研究正逐步深入。根据低渗透、非均质岩心的特点,制作边长为1.5 cm的玻璃刻蚀模型,在油藏温压条件下,进行CO_(2)-水分散体系渗流实验。通过观察微气泡与油、水、岩石相互作用过程,获取气泡吸附能力、推动油膜能力、气泡弹性能量等数据,进而定量表征分析驱油效果。实验结果表明:微气泡与油界面结合,具有特殊的吸附油膜现象,与水驱、气驱等作用机理显著不同。驱替过程相邻气泡间的合并也促进了油膜汇聚,同时微气泡的合并有助于气泡的流动,使吸附在气泡表面的油膜随气泡运移。微气泡运移时,气泡体积因压力降低而膨胀,所释放的弹性能量能够推动吸附在壁面的油膜运移。此外,采用Volume of Fluid多相流模型,对水气分散体系中微气泡推动油膜的运移过程进行模拟及分析,得到驱替油膜的主要因素是微气泡形变产生的弹性能量和微气泡自身的能量。气泡的能量作用在气泡前缘,通过与油膜表面接触产生推动作用。展开更多
基金Fundamental Research Funds for the Central Universities,Grant/Award Number:WK2060000016National Natural Science Foundation of China,Grant/Award Numbers:12222508,U1932213+2 种基金Youth Innovation Promotion Association of the Chinese Academy of Sciences,Grant/Award Number:2020454USTC Research Funds of the Double First‐Class Initiative,Grant/Award Number:YD2310002005National Key R&D Program of China,Grant/Award Number:2023YFA1506304。
文摘The key to designing photocatalysts is to orient the migration of photogenerated electrons to the target active sites rather than dissipate at inert sites.Herein,we demonstrate that the doping of phosphorus(P)significantly enriches photogenerated electrons at Ni active sites and enhances the performance for CO_(2) reduction into syngas.During photocatalytic CO_(2) reduction,Ni single‐atom‐anchored P‐modulated carbon nitride showed an impressive syngas yield rate of 85μmol gcat^(−1)h^(−1) and continuously adjustable CO/H_(2) ratios ranging from 5:1 to 1:2,which exceeded those of most of the reported carbon nitride‐based single‐atom catalysts.Mechanistic studies reveal that P doping improves the conductivity of catalysts,which promotes photogenerated electron transfer to the Ni active sites rather than dissipate randomly at low‐activity nonmetallic sites,facilitating the CO_(2)‐to‐syngas photoreduction process.
基金supported by the National Key R&D Program of China(2022YFA2105900)the National Natural Science Foundation of China(22178197)。
文摘Highly-efficient oxidation of 5-hydroxymethylfurtural(HMF) to 2,5-furandicarboxylic acid(FDCA) at low temperature with air as the oxidant is still challenging.Herein,inspired by the respirato ry electron transport chain(ETC) of living cells mediated by electron carriers,we constructed artificial ETCs and transformed liquid flow fuel cells(LFFCs) to flexible reactors for efficient oxidation of HMF to produce FDCA under mild conditions.This LFFC reactor employed an electrodeposition modified nickel foam as an anode to promote HMF oxidation and(VO_(2))_(2)SO_(4) as a cathode electron carrier to facilitate the electron transfer to air.The reaction rate could be easily controlled by selecting the anode catalyst,adjusting the external loading and changing the cathodic electron carrier or oxidants.A maximal power density of 44.9 mW cm^(-2) at room temperature was achieved,while for FDCA production,short-circuit condition was preferred to achieve quick transfer of electrons.For a single batch operation with 0.1 M initial HMF,FDCA yield reached 97.1%.By fed-batch operation,FDCA concentration reached 144.5 g L^(-1) with a total yield of 96%.Ni^(2+)/Ni^(3+) redox couple was the active species mediating the electron transfer,while both experimental and DFT calculation results indicated that HMFCA pathway was the preferred reaction mechanism.
基金supported by the National Natural Science Foundation of China(Grant no.42371136)the Guangdong Basic and Applied Basic Research Foundation(Grant no.2021B1515020032)the Innovation Group Project of Southern Marine Science and Engineering Guangdong Laboratory(Zhuhai)(Grant no.311022003).
文摘Offset-tracking is an essential method for deriving glacier flow rates using optical imagery.Sentinel-2(S2)and Landsat-8/9(L8/9)are popular optical satellites or constellations for polar studies,offering high spatial resolution with relatively short revisit time,wide swath width,and free accessibility.To evaluate and compare the precision of offset-tracking results yielded with these two kinds of data,in this study S2 and L8/9 imagery observed in Petermann Glacier in Greenland,Karakoram in High-Mountains Asia,and Amery Ice Shelf in the Antarctic are analyzed.Outliers and various systematic error sources in the offset-tracking results including orbital and strip errors were analyzed and eliminated at the pre-process stage.Precision at the off-glacier(bare rock)region was evaluated by presuming that no deformation occurred;then for both glacierized and the off-glacier regions,precision of velocity time series was evaluated based on error propagation theory.The least squares method based on connected components was used to solve flow rates time series based on multi-pair images offset-tracking.The results indicated that S2 achieved slightly higher precision than L8/9 in terms of both single-pair derived displacements and least square solved daily flow rates time series.Generally,the RMSE of daily velocity is 26%lower for S2 than L8/9.Moreover,S2 provided higher temporal resolution for monitoring glacier flow rates.
基金This research was conducted within the DECOVALEX-2023 projectDECOVALEX is an international research project comprising participants from industry,government,and academia,focusing on development of understanding,models and codes in complex coupled problems in sub-surface geological and engineering applications.DECOVALEX-2023 is the current phase of the project.The authors appreciate the DECOVALEX-2023 Funding Organisations Andra,BASE,BGE,BGR,CAS,CNSC,COVRA,US DOE,ENRESA,ENSI,JAEA,KAERI,NWMO,RWM,SÚRAO,SSM and Taipower for their financial and technical support of the work described in this paper.The statements made in the paper are,however,solely those of the authors and do not necessarily reflect those of the Funding Organisations.This work was further supported by the German Federal Ministry for Economic Affairs and Climate Action(BMWK).
文摘Dilatancy-controlled gas flow in preferential pathways plays a key role in the safety analysis of radioactive waste repositories.This is particularly the case for bentonite,an often-preferred barrier material.Gas flow in preferential pathways is characterized by localization and spontaneous behavior,which is challenging to simulate in numerical models due to strong hydro-mechanical coupling.To analyze a laboratory experiment in the framework of the DECOVALEX-2023 project,this study introduced a new approach of combining continuous modelling methods with spatial material properties derived from material heterogeneities and experimental observations.The proposed model utilized hydro-mechanical spatial distributions,namely Young’s modulus and gas entry pressure,and elastoplasticity combined with a linear swelling model.A conceptual strain-dependent permeability approach simulated dilatancycontrolled gas flow based on hydro-mechanical coupling.To test the effectiveness of the presented approach,a gas injection test in a compacted,saturated bentonite sample was simulated using the opensource code OpenGeoSys 5.8 and compared with experimental observations.The presented methodology is capable of simulating localized gas flow in preferential pathways.The spatial distributions of Young’s modulus and gas entry pressure affect the swelling pressure,relative permeability and,in combination with the strain-dependent permeability model,also the intrinsic permeability.
文摘水气分散体系驱油技术是针对低渗透油田采出程度低研发的新型提高采收率技术,目前已在长庆油田取得明显增油效果,但分散体系中微气泡与孔隙作用复杂,对其微观驱油机理的研究正逐步深入。根据低渗透、非均质岩心的特点,制作边长为1.5 cm的玻璃刻蚀模型,在油藏温压条件下,进行CO_(2)-水分散体系渗流实验。通过观察微气泡与油、水、岩石相互作用过程,获取气泡吸附能力、推动油膜能力、气泡弹性能量等数据,进而定量表征分析驱油效果。实验结果表明:微气泡与油界面结合,具有特殊的吸附油膜现象,与水驱、气驱等作用机理显著不同。驱替过程相邻气泡间的合并也促进了油膜汇聚,同时微气泡的合并有助于气泡的流动,使吸附在气泡表面的油膜随气泡运移。微气泡运移时,气泡体积因压力降低而膨胀,所释放的弹性能量能够推动吸附在壁面的油膜运移。此外,采用Volume of Fluid多相流模型,对水气分散体系中微气泡推动油膜的运移过程进行模拟及分析,得到驱替油膜的主要因素是微气泡形变产生的弹性能量和微气泡自身的能量。气泡的能量作用在气泡前缘,通过与油膜表面接触产生推动作用。
