Efficient cathode-catalysts with multi-functional properties are essential for Li-CO_(2)battery,while the construction of them with simultaneously enhanced CO_(2)reduction and evolution kinetics is still challenging.H...Efficient cathode-catalysts with multi-functional properties are essential for Li-CO_(2)battery,while the construction of them with simultaneously enhanced CO_(2)reduction and evolution kinetics is still challenging.Here,a kind of hybrid nanosheets based on Ru nanoparticles,Fe-TAPP and grapheme oxide(GO)has been designed through a one-pot self-assembly strategy.The Ru,Fe-porphyrin and GO based hybrid nanosheets(denoted as Ru/Fe-TAPP@GO)with integrated multi-components offer characteristics of ultrathin thickness(~4 nm),high electro-redox property,uniformly dispersed morphology,and high electrical conductivity,etc.These features endow Ru/Fe-TAPP@GO with ultra-low overpotential(0.82 V)and fully reversible discharge/charge property with a high specific-capacity of 39,000 m Ah/g within 2.0-4.5 V at 100 m A/g,which are much superior to Ru@GO and Fe-TAPP@GO.The achieved performance was presented as one of the best cathode-catalysts reported to date.The synergistically enhanced activity originated from the integrated hybrid nanosheets may provide a new pathway for designing efficient cathode-catalysts for Li-CO_(2)batteries.展开更多
Submarine or sub-lacustrine lobe deposits are important reservoirs,but the fan fringe deposits form heterogeneities within deep water fan deposits.Fan fringe facies records the complex sediment gravity flow types.By u...Submarine or sub-lacustrine lobe deposits are important reservoirs,but the fan fringe deposits form heterogeneities within deep water fan deposits.Fan fringe facies records the complex sediment gravity flow types.By understanding of the bed types and flow mechanisms,we can identify the fan fringe deposit,which aids in the reconstruction of deep water fan and reservoir evaluations.The Jiucaiyuanzi and Dalongkou sections in the West Bogda Mountains preserve well-exposed 536-m and 171-m thick successions,respectively,of a deep water lacustrine depositional system from the Middle Permian Lucaogou Formation.Bed types of the Lucaogou Formation include high-density turbidite,low-density turbidite,incomplete Bouma-type turbidite,hybrid event beds,and slump deposits.The Lucaogou Formation is interpreted here as a fan fringe facies due to the thin bed thickness that characterize turbidites and hybrid event beds,as well as the predominance of the isolated sheet architecture.Previous studies suggest that these deposits were considered as deposited in a deep water setting due to the absence of wave-related structures.The presence of abundant mud clasts in massive medium-coarse grained sandstone beds reflects the significant erosional capability and interactions between high-density turbidity currents and lake floor.The fan fringe facies here contains amalgamated and thick-bedded homolithic facies(~30%)and thin-bedded heterolithic facies(~70%).The examination of the bed type is of wider significance for facies prediction and reservoir heterogeneity in the sub-lacustrine fan fringe facies.展开更多
Bimetallic catalysts usually exhibit better performance than monometallic catalysts due to synergistic effect.However,there is a lack of exploring the synergistic effect on catalytic performance caused by the introduc...Bimetallic catalysts usually exhibit better performance than monometallic catalysts due to synergistic effect.However,there is a lack of exploring the synergistic effect on catalytic performance caused by the introduction of inactive metal ion.In this work,we design a molecular model system that can precisely regulate the metal site number and catalytic property.When these molecular metal compounds are used as homogeneous catalysts for photocatalytic CO_(2)reduction,the dinuclear heterometallic CuNi-L2shows the highest CO_(2)-to-CO conversion,which is 2.1 and 3.0 times higher than that of dinuclear homometallic Ni2-L2and mononuclear Ni-L1.Density functional theory calculations demonstrate that,in CuNi-L2,the introduction of inactive CuⅡis easier to promote the photo-generated electrons transferring to the coupled active NiⅡsite to achieve the highest activity.In addition,this work also provides insights to design and construct more efficient bimetallic catalysts in future.展开更多
A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphe...A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphen-pockets have been implanted into phthalocyanine(Pc)-based COFs through the elaborate design of structural struts;the produced NiPc-DFP-M COFs(M=Ni and Co)possess the advantages of controllable bimetallic centers with different coordination environments,outstanding light sensitivity,and built-in electric-field effects that can be successfully applied in light-assisted CO_(2)electroreduction.Notably,the optimal heterometallic NiPc-DFP-Co COF presents a∼100%Faradic efficiency for CO formation(FECO)in a wide potential range of−0.7 to−1.1 V and∼70%energy efficiency(−0.7 V)under light-irradiation,which is superior to mono-and homometallic COFs and under dark conditions.The high performance can be ascribed to the synergistic effect of the NiPc and Co-salphen pockets that can largely reduce the rate-determining energy-barrier and enhance the electron density to boost the light-assisted activity as supported by density functional theory calculations.A series of bimetallic Pc-based NiPc-DFP-M COF(M=Ni and Co)with integrated salphen-pockets and NiPc units have been synthesized and successfully applied in efficient light-assisted CO_(2)electroreduction.展开更多
Junggar Basin,located in northern Xinjiang,presents continuous and multikilometer-thick strata of the Jurassic deposits.The Jurassic was entirely terrestrial fluvial and lacustrine deltaic sedimentation.Eight outcrop ...Junggar Basin,located in northern Xinjiang,presents continuous and multikilometer-thick strata of the Jurassic deposits.The Jurassic was entirely terrestrial fluvial and lacustrine deltaic sedimentation.Eight outcrop sections across the Jurassic strata were measured at a resolution of meters in southern Junggar Basin.Controlling factors of sedimentary evolution and palaeoclimate changes in Junggar Basin during the Jurassic were discussed based on lithology,fossils and tectonic setting.In the Early to Middle Jurassic,the warm and wide Tethys Sea generated a strong monsoonal circulation over the central Asian continent,and provided adequate moisture for Junggar Basin.Coal-bearing strata of the Badaowan,Sangonghe,and Xishanyao Formations were developed under warm and humid palaeoclimate in Junggar Basin.In the late Middle Jurassic,Junggar Basin was in a semi-humid and semi-arid environment due to global warming event.Stratigraphy in the upper part of the Middle Jurassic with less plant fossils became multicolor or reddish from dark color sediments.During the Late Jurassic,collision of Lhasa and Qiangtang Block obstructed monsoon from the Tethys Sea.A major change in climate from semi-humid and semi-arid to arid conditions took place,and reddish strata of the Upper Jurassic were developed across Junggar Basin.展开更多
Polyester plastics such as poly(ethylene terephthal-ate)(PET)are utilized commonly in everyday life,yet only a small portion of these plastics are recycled,and typically,the recycling procedures face energy or polluti...Polyester plastics such as poly(ethylene terephthal-ate)(PET)are utilized commonly in everyday life,yet only a small portion of these plastics are recycled,and typically,the recycling procedures face energy or pollution problems.展开更多
It is well known that the low-valent Cu species are important catalytically active centers in the reduction of CO_(2) to hydrocarbon products.However,the Cu(l)-based catalysts are easily reduced during the electroredu...It is well known that the low-valent Cu species are important catalytically active centers in the reduction of CO_(2) to hydrocarbon products.However,the Cu(l)-based catalysts are easily reduced during the electroreduction of CO_(2),which causes phase transformation of catalysts and leads to a decrease of intrinsic catalytic activity.Therefore,it is of great significance to synthesize Cu(l)-based catalysts with specific interactions that can keep the catalytically active Cu sites stable in the electrocatalytic process.Based on the above considerations,a hexanuclear Cu cluster with strong cuprophilic interactions has been designed and utilized as a secondary building unit(SBU)to construct a stable metal-organic framework(MOF)electrocatalyst(NNU-50).As expected,the NNU-50 has served as an effective electrocatalyst for the CO_(2)-to-CH4 conversion by exhibiting a high Faradaic efficiency for CH4(FEcH4)of 66.40%and a large current density of~400 mA·cm-2 at-1.0 V vs.reversible hydrogen electrode(RHE),which is one of the best catalytic performances among the stable MOF electrocatalysts until now.This work contributes more ideas for the design of stable and efficient MOF-based electrocatalysts for CO_(2) reduction reaction.展开更多
Electrocatalytic CO_(2) reduction(ECR)to high value-added chemicals by using renewable electricity presents a promising strategy to realize“carbon neutrality”.However,the ECR system is still limited by its low curre...Electrocatalytic CO_(2) reduction(ECR)to high value-added chemicals by using renewable electricity presents a promising strategy to realize“carbon neutrality”.However,the ECR system is still limited by its low current density and poor CO_(2) utilization efficiency.Herein,by using the confinement effect of covalent organic frame-works(COFs)to confine the in-situ growth of metal nanoclusters(NCs),we develop a series of Cu NCs encap-sulated on COF catalysts(Cu-NC@COF)for ECR.Among them,Cu-NC@CuPc-COF as a gas diffusion electrode(GDE)achieves a maximum CO_(2)-to-CH_(4) Faradaic efficiency of 74±3%(at-1.0 V vs.Reversible Hydrogen Electrode(RHE))with a current density of 538±31 mA cm^(-2)(at-1.2 V vs.RHE)in a flow cell,making it one of the best among reported materials.More importantly,the current density is much higher than the relevant industrial current density(200 mA cm^(-2)),indicating the potential for industrial application.This work opens up new possibilities for the design of ECR catalysts that utilize synergistic strategy.展开更多
Morphology-controlled electrocatalysts with the ability of CO_(2) adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO_(2) reduction reaction (CO_(2)RR). Here, three...Morphology-controlled electrocatalysts with the ability of CO_(2) adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO_(2) reduction reaction (CO_(2)RR). Here, three kinds of multi-dimensional nanostructures (i.e., hollow sphere, nanosheets and nanofibers) have been successfully produced through the modulation of porphyrin-based covalent organic frameworks (COFs) with various modulators. The obtained nanostructures with high-stability, large surface-area, and single metal sites enable efficient CO_(2)RR into CH_(4). Notably, they all exhibit higher FE (hollow sphere, 68.2%;nanosheet, 64.2% and nanofiber, 71.0%, -0.9 V) than COF-366-Cu (43.0%, -0.9 V) after morphology control. Noteworthy, the FE of COF-366-Cu (HS) keeps higher than 52.4% over a wide potential range from -0.9 V to -1.1 V and the achieved FECH_(4) + C_(2)H_(4) (82.8%, -0.9 V) is superior to most of reported COFs and copper-based electrocatalysts. This work paves a new way in the exploration of COF-based multi-dimensional nanostructures applicable in efficient CO_(2)RR to CH_(4).展开更多
基金financially supported by the National Natural Science Foundation of China(NSFC,Nos.21871141,21871142,21901122,22071109,22105080,22171139 and 92061101)the Excellent Youth Foundation of Jiangsu Natural Science Foundation(No.BK20211593)+1 种基金Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials。
文摘Efficient cathode-catalysts with multi-functional properties are essential for Li-CO_(2)battery,while the construction of them with simultaneously enhanced CO_(2)reduction and evolution kinetics is still challenging.Here,a kind of hybrid nanosheets based on Ru nanoparticles,Fe-TAPP and grapheme oxide(GO)has been designed through a one-pot self-assembly strategy.The Ru,Fe-porphyrin and GO based hybrid nanosheets(denoted as Ru/Fe-TAPP@GO)with integrated multi-components offer characteristics of ultrathin thickness(~4 nm),high electro-redox property,uniformly dispersed morphology,and high electrical conductivity,etc.These features endow Ru/Fe-TAPP@GO with ultra-low overpotential(0.82 V)and fully reversible discharge/charge property with a high specific-capacity of 39,000 m Ah/g within 2.0-4.5 V at 100 m A/g,which are much superior to Ru@GO and Fe-TAPP@GO.The achieved performance was presented as one of the best cathode-catalysts reported to date.The synergistically enhanced activity originated from the integrated hybrid nanosheets may provide a new pathway for designing efficient cathode-catalysts for Li-CO_(2)batteries.
基金The study was funded by National Science and Technology Major Project(Grant No.2017ZX05001-002)National Natural Science Foundation of China(Grant No.41802129)。
文摘Submarine or sub-lacustrine lobe deposits are important reservoirs,but the fan fringe deposits form heterogeneities within deep water fan deposits.Fan fringe facies records the complex sediment gravity flow types.By understanding of the bed types and flow mechanisms,we can identify the fan fringe deposit,which aids in the reconstruction of deep water fan and reservoir evaluations.The Jiucaiyuanzi and Dalongkou sections in the West Bogda Mountains preserve well-exposed 536-m and 171-m thick successions,respectively,of a deep water lacustrine depositional system from the Middle Permian Lucaogou Formation.Bed types of the Lucaogou Formation include high-density turbidite,low-density turbidite,incomplete Bouma-type turbidite,hybrid event beds,and slump deposits.The Lucaogou Formation is interpreted here as a fan fringe facies due to the thin bed thickness that characterize turbidites and hybrid event beds,as well as the predominance of the isolated sheet architecture.Previous studies suggest that these deposits were considered as deposited in a deep water setting due to the absence of wave-related structures.The presence of abundant mud clasts in massive medium-coarse grained sandstone beds reflects the significant erosional capability and interactions between high-density turbidity currents and lake floor.The fan fringe facies here contains amalgamated and thick-bedded homolithic facies(~30%)and thin-bedded heterolithic facies(~70%).The examination of the bed type is of wider significance for facies prediction and reservoir heterogeneity in the sub-lacustrine fan fringe facies.
基金financially supported by the National Natural Science Foundation of China(NSFC,Nos.92061101,21871141,21871142 and 22071109)Project funded by China Postdoctoral Science Foundation(No.2018M630572)。
文摘Bimetallic catalysts usually exhibit better performance than monometallic catalysts due to synergistic effect.However,there is a lack of exploring the synergistic effect on catalytic performance caused by the introduction of inactive metal ion.In this work,we design a molecular model system that can precisely regulate the metal site number and catalytic property.When these molecular metal compounds are used as homogeneous catalysts for photocatalytic CO_(2)reduction,the dinuclear heterometallic CuNi-L2shows the highest CO_(2)-to-CO conversion,which is 2.1 and 3.0 times higher than that of dinuclear homometallic Ni2-L2and mononuclear Ni-L1.Density functional theory calculations demonstrate that,in CuNi-L2,the introduction of inactive CuⅡis easier to promote the photo-generated electrons transferring to the coupled active NiⅡsite to achieve the highest activity.In addition,this work also provides insights to design and construct more efficient bimetallic catalysts in future.
基金supported by National Natural Science Foundation of China(grant nos.21871141,21871142,22071109,21901122,22225109,22171139).
文摘A strategy that enables introducing bimetallic active sites is desired for the exploration of light-sensitive covalent organic framework(COF)-based electrocatalysts in light-assisted CO_(2)electroreduction.Here,salphen-pockets have been implanted into phthalocyanine(Pc)-based COFs through the elaborate design of structural struts;the produced NiPc-DFP-M COFs(M=Ni and Co)possess the advantages of controllable bimetallic centers with different coordination environments,outstanding light sensitivity,and built-in electric-field effects that can be successfully applied in light-assisted CO_(2)electroreduction.Notably,the optimal heterometallic NiPc-DFP-Co COF presents a∼100%Faradic efficiency for CO formation(FECO)in a wide potential range of−0.7 to−1.1 V and∼70%energy efficiency(−0.7 V)under light-irradiation,which is superior to mono-and homometallic COFs and under dark conditions.The high performance can be ascribed to the synergistic effect of the NiPc and Co-salphen pockets that can largely reduce the rate-determining energy-barrier and enhance the electron density to boost the light-assisted activity as supported by density functional theory calculations.A series of bimetallic Pc-based NiPc-DFP-M COF(M=Ni and Co)with integrated salphen-pockets and NiPc units have been synthesized and successfully applied in efficient light-assisted CO_(2)electroreduction.
基金supported by PetroChina Xinjiang Oilfield Companythe Chinese National Natural Science Fund Project(No.41072084+2 种基金No.41272132)National Program on Key Basic Research Project(973 Program)(No.2009CB219502-3)the Fundamental Research Funds for the central universities(2-9-2013-97)
文摘Junggar Basin,located in northern Xinjiang,presents continuous and multikilometer-thick strata of the Jurassic deposits.The Jurassic was entirely terrestrial fluvial and lacustrine deltaic sedimentation.Eight outcrop sections across the Jurassic strata were measured at a resolution of meters in southern Junggar Basin.Controlling factors of sedimentary evolution and palaeoclimate changes in Junggar Basin during the Jurassic were discussed based on lithology,fossils and tectonic setting.In the Early to Middle Jurassic,the warm and wide Tethys Sea generated a strong monsoonal circulation over the central Asian continent,and provided adequate moisture for Junggar Basin.Coal-bearing strata of the Badaowan,Sangonghe,and Xishanyao Formations were developed under warm and humid palaeoclimate in Junggar Basin.In the late Middle Jurassic,Junggar Basin was in a semi-humid and semi-arid environment due to global warming event.Stratigraphy in the upper part of the Middle Jurassic with less plant fossils became multicolor or reddish from dark color sediments.During the Late Jurassic,collision of Lhasa and Qiangtang Block obstructed monsoon from the Tethys Sea.A major change in climate from semi-humid and semi-arid to arid conditions took place,and reddish strata of the Upper Jurassic were developed across Junggar Basin.
基金This work was supported financially by National Nature Science Foundation of China(NSFC)(nos.21622104,21701085,21871125,21871141,21871142,and 21901122)The National Science Foundation(NSF)of Jiangsu Province of China(no.BK20171032)+2 种基金the Natural Science Research of Jiangsu Higher Education Institutions of China(nos.17KJB150025 and 19KJB150011)Project funded by China Postdoctoral Science Foundation(nos.2018M630572 and 2019M651873)Priority Academ-ic Program Development of Jiangsu Higher Education Institutions and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.
文摘Polyester plastics such as poly(ethylene terephthal-ate)(PET)are utilized commonly in everyday life,yet only a small portion of these plastics are recycled,and typically,the recycling procedures face energy or pollution problems.
基金financially supported by the National Natural Science Foundation of China(Nos.21871141,21871142,22071109,22105080,and 92061101)the Excellent Youth Foundation of Jiangsu Natural Science Foundation(No.BK20211593)Priority Academic Program Development of Jiangsu Higher Education Institutions,and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.
文摘It is well known that the low-valent Cu species are important catalytically active centers in the reduction of CO_(2) to hydrocarbon products.However,the Cu(l)-based catalysts are easily reduced during the electroreduction of CO_(2),which causes phase transformation of catalysts and leads to a decrease of intrinsic catalytic activity.Therefore,it is of great significance to synthesize Cu(l)-based catalysts with specific interactions that can keep the catalytically active Cu sites stable in the electrocatalytic process.Based on the above considerations,a hexanuclear Cu cluster with strong cuprophilic interactions has been designed and utilized as a secondary building unit(SBU)to construct a stable metal-organic framework(MOF)electrocatalyst(NNU-50).As expected,the NNU-50 has served as an effective electrocatalyst for the CO_(2)-to-CH4 conversion by exhibiting a high Faradaic efficiency for CH4(FEcH4)of 66.40%and a large current density of~400 mA·cm-2 at-1.0 V vs.reversible hydrogen electrode(RHE),which is one of the best catalytic performances among the stable MOF electrocatalysts until now.This work contributes more ideas for the design of stable and efficient MOF-based electrocatalysts for CO_(2) reduction reaction.
基金This work was financially supported by the NSFC(Nos.22225109,22071109,22105080 and 22201083)the Project funded by the China Postdoctoral Science Foundation(Nos.2020M682747 and 2021M701270)+2 种基金the Guangdong Basic and Applied Basic Research Foundation(Grant 2023A1515010779 and 2023A1515010928)the Guangzhou Basic and Applied Basic Research Fund Project(Grant 202102020209)China National Postdoctoral Program for Innovative Talents(BX20220115).
文摘Electrocatalytic CO_(2) reduction(ECR)to high value-added chemicals by using renewable electricity presents a promising strategy to realize“carbon neutrality”.However,the ECR system is still limited by its low current density and poor CO_(2) utilization efficiency.Herein,by using the confinement effect of covalent organic frame-works(COFs)to confine the in-situ growth of metal nanoclusters(NCs),we develop a series of Cu NCs encap-sulated on COF catalysts(Cu-NC@COF)for ECR.Among them,Cu-NC@CuPc-COF as a gas diffusion electrode(GDE)achieves a maximum CO_(2)-to-CH_(4) Faradaic efficiency of 74±3%(at-1.0 V vs.Reversible Hydrogen Electrode(RHE))with a current density of 538±31 mA cm^(-2)(at-1.2 V vs.RHE)in a flow cell,making it one of the best among reported materials.More importantly,the current density is much higher than the relevant industrial current density(200 mA cm^(-2)),indicating the potential for industrial application.This work opens up new possibilities for the design of ECR catalysts that utilize synergistic strategy.
基金supported by the National Natural Science Foundation of China(21871141,21871142,21901122,22071109 and 92061101)the Natural Science Research of Jiangsu Higher Education Institutions of China(19KJB150011)+3 种基金China Postdoctoral Science Foundation(2018M630572 and 2019M651873)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX201171)Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials.
基金financially supported by the National Natural Science Foundation of China(21622104,21871142 and 21901122)the Natural Science Foundation of Jiangsu Province of China(BK20171032)+3 种基金the Natural Science Research of Jiangsu Higher Education Institutions of China(17KJB150025 and 19KJB150011)Projects funded by China Postdoctoral Science Foundation(2018 M630572 and 2019 M651873)Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials。
基金financially supported by the National Natural Science Foundation of China (NSFC, Nos. 21871141, 21871142,21901122, 22071109 and 92061101)the Natural Science Research of Jiangsu Higher Education Institutions of China (No.19KJB150011)+1 种基金Project funded by China Postdoctoral Science Foundation (Nos. 2018M630572 and 2019M651873)Priority Academic Program Development of Jiangsu Higher Education Institutions and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials。
文摘Morphology-controlled electrocatalysts with the ability of CO_(2) adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO_(2) reduction reaction (CO_(2)RR). Here, three kinds of multi-dimensional nanostructures (i.e., hollow sphere, nanosheets and nanofibers) have been successfully produced through the modulation of porphyrin-based covalent organic frameworks (COFs) with various modulators. The obtained nanostructures with high-stability, large surface-area, and single metal sites enable efficient CO_(2)RR into CH_(4). Notably, they all exhibit higher FE (hollow sphere, 68.2%;nanosheet, 64.2% and nanofiber, 71.0%, -0.9 V) than COF-366-Cu (43.0%, -0.9 V) after morphology control. Noteworthy, the FE of COF-366-Cu (HS) keeps higher than 52.4% over a wide potential range from -0.9 V to -1.1 V and the achieved FECH_(4) + C_(2)H_(4) (82.8%, -0.9 V) is superior to most of reported COFs and copper-based electrocatalysts. This work paves a new way in the exploration of COF-based multi-dimensional nanostructures applicable in efficient CO_(2)RR to CH_(4).
