Nanoscale electrocatalysts have exhibited promising activity and stability,improving the kinetics of numerous electrochemical reactions in renewable energy systems such as electrolyzers,fuel cells,and metal-air batter...Nanoscale electrocatalysts have exhibited promising activity and stability,improving the kinetics of numerous electrochemical reactions in renewable energy systems such as electrolyzers,fuel cells,and metal-air batteries.Due to the size effect,nano particles with extreme small size have high surface areas,complicated morphology,and various surface terminations,which make them different from their bulk phases and often undergo restructuring during the reactions.These restructured materials are hard to probe by conventional ex-situ characterizations,thus leaving the true reaction centers and/or active sites difficult to determine.Nowadays,in situ techniques,particularly X-ray absorption spectroscopy(XAS),have become an important tool to obtain oxidation states,electronic structure,and local bonding environments,which are critical to investigate the electrocatalysts under real reaction conditions.In this review,we go over the basic principles of XAS and highlight recent applications of in situ XAS in studies of nanoscale electrocatalysts.展开更多
Fe-based single-atomic site catalysts(SASCs),with the natural metalloproteases-like active site structure,have attracted widespread attention in biocatalysis and biosensing.Precisely,controlling the isolated single-at...Fe-based single-atomic site catalysts(SASCs),with the natural metalloproteases-like active site structure,have attracted widespread attention in biocatalysis and biosensing.Precisely,controlling the isolated single-atom Fe-N-C active site structure is crucial to improve the SASCs’performance.In this work,we use a facile ion-imprinting method(IIM)to synthesize isolated Fe-N-C single-atomic site catalysts(IIM-Fe-SASC).With this method,the ion-imprinting process can precisely control ion at the atomic level and form numerous well-defined single-atomic Fe-N-C sites.The IIM-Fe-SASC shows better peroxidase-like activities than that of non-imprinted references.Due to its excellent properties,IIM-Fe-SASC is an ideal nanoprobe used in the colorimetric biosensing of hydrogen peroxide(H_(2)O_(2)).Using IIM-Fe-SASC as the nanoprobe,in situ detection of H_(2)O_(2)generated from MDA-MB-231 cells has been successfully demonstrated with satisfactory sensitivity and specificity.This work opens a novel and easy route in designing advanced SASC and provides a sensitive tool for intracellular H_(2)O_(2)detection.展开更多
Here we demonstrate a theory-driven, novel dual-shell coating system of Li_(2)SrSiO_(4) and Al_(2)O_(3), achieved via a facile and scalable sol-gel technique on LiCoO_(2) electrode particles. The optimal thickness of ...Here we demonstrate a theory-driven, novel dual-shell coating system of Li_(2)SrSiO_(4) and Al_(2)O_(3), achieved via a facile and scalable sol-gel technique on LiCoO_(2) electrode particles. The optimal thickness of each coating can lead to increased specific capacity(~185 m Ah/g at 0.5 C-rate) at a cut-off potential of 4.5 V, and greater cycling stability at very high C rates(up to 10 C) in half-cells with lithium metal. The mechanism of this superior performance was investigated using a combination of X-ray and electron characterization methods. It shows that the results of this investigation can inform future studies to identify still better dual-shell coating schemes, achieved by such industrially feasible techniques, for application on similar, nickel-rich cathode materials.展开更多
The ocean is an important inventory of anthropogenic mercury(Hg),yet the history of anthropogenic Hg accumulation in the ocean remains largely unexplored.Deep-sea corals are an emerging archive of past ocean chemistry...The ocean is an important inventory of anthropogenic mercury(Hg),yet the history of anthropogenic Hg accumulation in the ocean remains largely unexplored.Deep-sea corals are an emerging archive of past ocean chemistry,which take in sinking or suspended particulate organic matter as their food sources.Such organic matter would exchange Hg with the local seawater before being consumed by the deepsea corals.As such,the organics preserved in the coral skeleton may record the Hg evolution of the ambient seawater during the time of coral growth.Here,we report the first data on Hg concentrations variability of a deep-sea proteinaceous coral in the oligotrophic North Pacific at the water depth of 1249 m,in attempt to understand the transfer of anthropogenic Hg into the deep Pacific ocean over the last seven centuries.We find that the Hg concentrations of different coral growth layers have remained relatively constant albeit with considerable short-term variability through time.The overall stable Hg concentration of the last seven centuries recorded in our sample suggests that anthropogenic pollution is not yet a clearly resolvable component in the deep oligotrophic North Pacific waters,in agreement with rece nt estimation from modelling works and observational studies of modern seawater profiles.As there is hardly an unambiguous way to separate anthropogenic Hg from the natural background based on recent seawater profiles,our historical data provide valuable information helping to understand the oceanic cycle of Hg through time.展开更多
Lithium-ion batteries(LIBs) as energy storage devices play an important role in all aspects of our life. The increasing energy demand of the society requires LIBs with higher energy density and better performance. We ...Lithium-ion batteries(LIBs) as energy storage devices play an important role in all aspects of our life. The increasing energy demand of the society requires LIBs with higher energy density and better performance. We here develop a new and easy-to-scaleup sol-gel method to coat a surface protection layer on commercial LiCoO2cathode. We demonstrate that a proper thickness can improve the cycling life with a higher cut-off potential(4.5 V), larger energy capacity(180 mAh/g at 0.5 C) and better energy density(35% more compared to non-coated LiCoO2). The mechanism of the protection layer is also revealed by a combination of electron microscopy and synchrotron X-ray spectroscopy.展开更多
Single-atom nanozymes(SANs)possess unique features of maximum atomic utilization and present highly assembled enzyme-like structure and remarkable enzyme-like activity.By introducing SANs into immunoassay,limitations ...Single-atom nanozymes(SANs)possess unique features of maximum atomic utilization and present highly assembled enzyme-like structure and remarkable enzyme-like activity.By introducing SANs into immunoassay,limitations of ELISA such as low stability of horseradish peroxidase(HRP)can be well addressed,thereby improving the performance of the immunoassays.In this work,we have developed novel Fe-N-C single-atom nanozymes(Fe-N_(x)SANs)derived from Fe-doped polypyrrole(PPy)nanotube and substituted the enzymes in ELISA kit for enhancing the detection sensitivity of amyloid beta 1-40.Results indicate that the Fe-N_(x)SANs contain high density of single-atom active sites and comparable enzyme-like properties as HRP,owing to the maximized utilization of Fe atoms and their abundant active sites,which could mimic natural metalloproteases structures.Further designed SAN-linked immunosorbent assay(SAN-LISA)demonstrates the ultralow limit of detection(LOD)of 0.88 pg/mL,much more sensitive than that of commercial ELISA(9.98 pg/mL).The results confirm that the Fe-N_(x)SANs can serve as a satisfactory replacement of enzyme labels,which show great potential as an ultrasensitive colorimetric immunoassay.展开更多
Iron(Fe)is a productivity-limiting nutrient in the ocean.However,the sources of dissolved Fe(dFe)in the deep ocean and how they respond to tectonic and climate changes are still poorly understood.In the northern hemis...Iron(Fe)is a productivity-limiting nutrient in the ocean.However,the sources of dissolved Fe(dFe)in the deep ocean and how they respond to tectonic and climate changes are still poorly understood.In the northern hemisphere,dust flux to the low-latitude western Pacific has increased dramatically since the late Miocene associated with intense aridification of the Asian inland.Meanwhile,the terrigenous material supply to the open ocean might have also changed as a result of the reorganization of the Pacific circulation due to the gradual closure of seaways in the low latitudes.Therefore,the western Pacific is a characteristic region for understanding the sources of dFe in the deep ocean and their responses to long term climate changes.Here,we present data on isotopic evolution of dFe and dissolved Pb since^8 Ma based on ferromanganese crust METG-03(16.0°N,152.0°E,3850 m water depth)in the western Pacific deep water.Our results show thatδ56Fe of the crust remains fairly stable since the late Miocene,i.e.,about-0.32±0.08‰(2SD).We infer thatδ56Fe of dFe in the deep western Pacific is relatively invariant at^0.45±0.1‰based on the Fe isotopic fractionation between hydrogenetic crust and the seawater dissolved component.The reconstructed isotope signature is similar to the measuredδ56Fe value(0.37±0.15‰)of the intermediate to deep waters in the modern low-latitude western Pacific region close to the island arcs,but is significantly higher than that of the eastern Pacific deep waters near South America which is controlled by the reductive dissolution of continental shelf sediments and the hydrothermal inputs(δ56Fe<-0.1‰).The deep-water 206Pb/204Pb ratio recorded by METG-03 displays systematic increase at about 8–4 Ma,reflecting increased input from sediment dissolution of low-latitude island arcs associated with reorganization of the western Pacific deep circulation.Notably,Fe isotopes of terrigenous materials from different sources are similar,while their dissolved Fe isotopic signatures released to the ocean are mainly controlled by the mechanism of particle dissolution.The stability ofδ56Fe and systematic changes in Pb isotopes over the last^8 Ma thus suggest that Asian dust dissolution and hydrothermal inputs are likely only minor sources of dFe in the low-latitude deep western Pacific,while the acquisition and transport of dFe from shelf sediments by organic ligand binding in the oxic environment is the major dFe source which keeps stable on tectonic time scales since the late Miocene.展开更多
Main observation and conclusion Inspired by the nitrogen fixation process on MoFe nitrogenase,asymmetrical coordinated Fe grafted onto 1T MoS_(2) were successfully synthesized.The unique electron-rich structure with a...Main observation and conclusion Inspired by the nitrogen fixation process on MoFe nitrogenase,asymmetrical coordinated Fe grafted onto 1T MoS_(2) were successfully synthesized.The unique electron-rich structure with asymmetrical coordination made the 1T Fe_(0.1)Mo_(0.9)S_(2) layered material actively react with water and dinitrogen at room temperature and atmosphere pressure.展开更多
As an essential part of DC-Link in the power converter,capacitor plays a crucial role in absorbing ripple current and suppressing ripple voltage.The health and residual service life of the DC-Link capacitor is one of ...As an essential part of DC-Link in the power converter,capacitor plays a crucial role in absorbing ripple current and suppressing ripple voltage.The health and residual service life of the DC-Link capacitor is one of the decisive factors for the safety,stability,and efficiency of the system in which it is located.Aiming at the shortcomings of existing methods,such as low dynamic sensitivity of data update and fluctuation of identification results,a capacitor state identification method based on improved RLS is proposed in this paper.The proposed method is optimized by introducing the forgetting factor algorithm and root means square algorithm to modify the iterative formula and final identification results.Compared with existing methods,this method can identify the capacitor’s current state in real time and accurately.Finally,we successfully verified the accuracy,robustness,and adaptability of the proposed method by a series of experimental tests on a dSPACE platform.展开更多
基金financially supported by start-up funds from Oregon State UniversityPart of authors’ work using soft X-ray absorption spectroscopy was performed at beamline 6.3.1 of Advanced Light Source, which is an Office of Science User Facility operated for the U.S.DOE Office of Science by Lawrence Berkeley National Laboratory and supported by the DOE under Contract No. DEAC02-05CH11231
文摘Nanoscale electrocatalysts have exhibited promising activity and stability,improving the kinetics of numerous electrochemical reactions in renewable energy systems such as electrolyzers,fuel cells,and metal-air batteries.Due to the size effect,nano particles with extreme small size have high surface areas,complicated morphology,and various surface terminations,which make them different from their bulk phases and often undergo restructuring during the reactions.These restructured materials are hard to probe by conventional ex-situ characterizations,thus leaving the true reaction centers and/or active sites difficult to determine.Nowadays,in situ techniques,particularly X-ray absorption spectroscopy(XAS),have become an important tool to obtain oxidation states,electronic structure,and local bonding environments,which are critical to investigate the electrocatalysts under real reaction conditions.In this review,we go over the basic principles of XAS and highlight recent applications of in situ XAS in studies of nanoscale electrocatalysts.
基金This work was supported by a WSU startup fund.XAS measurements were done at beamline 12-BM of the Advanced Photon Source(APS),which is a User Facility operated for the U.S.Department of Energy Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357.
文摘Fe-based single-atomic site catalysts(SASCs),with the natural metalloproteases-like active site structure,have attracted widespread attention in biocatalysis and biosensing.Precisely,controlling the isolated single-atom Fe-N-C active site structure is crucial to improve the SASCs’performance.In this work,we use a facile ion-imprinting method(IIM)to synthesize isolated Fe-N-C single-atomic site catalysts(IIM-Fe-SASC).With this method,the ion-imprinting process can precisely control ion at the atomic level and form numerous well-defined single-atomic Fe-N-C sites.The IIM-Fe-SASC shows better peroxidase-like activities than that of non-imprinted references.Due to its excellent properties,IIM-Fe-SASC is an ideal nanoprobe used in the colorimetric biosensing of hydrogen peroxide(H_(2)O_(2)).Using IIM-Fe-SASC as the nanoprobe,in situ detection of H_(2)O_(2)generated from MDA-MB-231 cells has been successfully demonstrated with satisfactory sensitivity and specificity.This work opens a novel and easy route in designing advanced SASC and provides a sensitive tool for intracellular H_(2)O_(2)detection.
基金supported by the U.S. National Science Foundation (CBET-1949870, CBET-2016192, and DMR-1832803)Part of the research was conducted at the Northwest Nanotechnology Infrastructure, a National Nanotechnology Coordinated Infrastructure (NNCI) site at Oregon State University, which is supported, in part, by the U.S. National Science Foundation (NNCI-1542101 and NCC-2025489), and Oregon State University。
文摘Here we demonstrate a theory-driven, novel dual-shell coating system of Li_(2)SrSiO_(4) and Al_(2)O_(3), achieved via a facile and scalable sol-gel technique on LiCoO_(2) electrode particles. The optimal thickness of each coating can lead to increased specific capacity(~185 m Ah/g at 0.5 C-rate) at a cut-off potential of 4.5 V, and greater cycling stability at very high C rates(up to 10 C) in half-cells with lithium metal. The mechanism of this superior performance was investigated using a combination of X-ray and electron characterization methods. It shows that the results of this investigation can inform future studies to identify still better dual-shell coating schemes, achieved by such industrially feasible techniques, for application on similar, nickel-rich cathode materials.
基金the National Natural Science Foundation of China (Nos.41822603,41991325,41930533)the Strategic Priority Research Program of Chinese Academy of Sciences (No.XDB40010200)+1 种基金the Fundamental Research Funds for the Central Universities (No.0206-14380125)the Frontiers Science Center for Critical Earth Material Cycling Fund (No.DLTD2102)。
文摘The ocean is an important inventory of anthropogenic mercury(Hg),yet the history of anthropogenic Hg accumulation in the ocean remains largely unexplored.Deep-sea corals are an emerging archive of past ocean chemistry,which take in sinking or suspended particulate organic matter as their food sources.Such organic matter would exchange Hg with the local seawater before being consumed by the deepsea corals.As such,the organics preserved in the coral skeleton may record the Hg evolution of the ambient seawater during the time of coral growth.Here,we report the first data on Hg concentrations variability of a deep-sea proteinaceous coral in the oligotrophic North Pacific at the water depth of 1249 m,in attempt to understand the transfer of anthropogenic Hg into the deep Pacific ocean over the last seven centuries.We find that the Hg concentrations of different coral growth layers have remained relatively constant albeit with considerable short-term variability through time.The overall stable Hg concentration of the last seven centuries recorded in our sample suggests that anthropogenic pollution is not yet a clearly resolvable component in the deep oligotrophic North Pacific waters,in agreement with rece nt estimation from modelling works and observational studies of modern seawater profiles.As there is hardly an unambiguous way to separate anthropogenic Hg from the natural background based on recent seawater profiles,our historical data provide valuable information helping to understand the oceanic cycle of Hg through time.
基金supported by Callahan Faculty Scholar Endowment Fund from Oregon State University,USA
文摘Lithium-ion batteries(LIBs) as energy storage devices play an important role in all aspects of our life. The increasing energy demand of the society requires LIBs with higher energy density and better performance. We here develop a new and easy-to-scaleup sol-gel method to coat a surface protection layer on commercial LiCoO2cathode. We demonstrate that a proper thickness can improve the cycling life with a higher cut-off potential(4.5 V), larger energy capacity(180 mAh/g at 0.5 C) and better energy density(35% more compared to non-coated LiCoO2). The mechanism of the protection layer is also revealed by a combination of electron microscopy and synchrotron X-ray spectroscopy.
基金This work was supported by a start-up fund from Washington State University.
文摘Single-atom nanozymes(SANs)possess unique features of maximum atomic utilization and present highly assembled enzyme-like structure and remarkable enzyme-like activity.By introducing SANs into immunoassay,limitations of ELISA such as low stability of horseradish peroxidase(HRP)can be well addressed,thereby improving the performance of the immunoassays.In this work,we have developed novel Fe-N-C single-atom nanozymes(Fe-N_(x)SANs)derived from Fe-doped polypyrrole(PPy)nanotube and substituted the enzymes in ELISA kit for enhancing the detection sensitivity of amyloid beta 1-40.Results indicate that the Fe-N_(x)SANs contain high density of single-atom active sites and comparable enzyme-like properties as HRP,owing to the maximized utilization of Fe atoms and their abundant active sites,which could mimic natural metalloproteases structures.Further designed SAN-linked immunosorbent assay(SAN-LISA)demonstrates the ultralow limit of detection(LOD)of 0.88 pg/mL,much more sensitive than that of commercial ELISA(9.98 pg/mL).The results confirm that the Fe-N_(x)SANs can serve as a satisfactory replacement of enzyme labels,which show great potential as an ultrasensitive colorimetric immunoassay.
基金supported by the National Natural Science Foundation of China(Grant Nos.91858105&41822603)。
文摘Iron(Fe)is a productivity-limiting nutrient in the ocean.However,the sources of dissolved Fe(dFe)in the deep ocean and how they respond to tectonic and climate changes are still poorly understood.In the northern hemisphere,dust flux to the low-latitude western Pacific has increased dramatically since the late Miocene associated with intense aridification of the Asian inland.Meanwhile,the terrigenous material supply to the open ocean might have also changed as a result of the reorganization of the Pacific circulation due to the gradual closure of seaways in the low latitudes.Therefore,the western Pacific is a characteristic region for understanding the sources of dFe in the deep ocean and their responses to long term climate changes.Here,we present data on isotopic evolution of dFe and dissolved Pb since^8 Ma based on ferromanganese crust METG-03(16.0°N,152.0°E,3850 m water depth)in the western Pacific deep water.Our results show thatδ56Fe of the crust remains fairly stable since the late Miocene,i.e.,about-0.32±0.08‰(2SD).We infer thatδ56Fe of dFe in the deep western Pacific is relatively invariant at^0.45±0.1‰based on the Fe isotopic fractionation between hydrogenetic crust and the seawater dissolved component.The reconstructed isotope signature is similar to the measuredδ56Fe value(0.37±0.15‰)of the intermediate to deep waters in the modern low-latitude western Pacific region close to the island arcs,but is significantly higher than that of the eastern Pacific deep waters near South America which is controlled by the reductive dissolution of continental shelf sediments and the hydrothermal inputs(δ56Fe<-0.1‰).The deep-water 206Pb/204Pb ratio recorded by METG-03 displays systematic increase at about 8–4 Ma,reflecting increased input from sediment dissolution of low-latitude island arcs associated with reorganization of the western Pacific deep circulation.Notably,Fe isotopes of terrigenous materials from different sources are similar,while their dissolved Fe isotopic signatures released to the ocean are mainly controlled by the mechanism of particle dissolution.The stability ofδ56Fe and systematic changes in Pb isotopes over the last^8 Ma thus suggest that Asian dust dissolution and hydrothermal inputs are likely only minor sources of dFe in the low-latitude deep western Pacific,while the acquisition and transport of dFe from shelf sediments by organic ligand binding in the oxic environment is the major dFe source which keeps stable on tectonic time scales since the late Miocene.
基金The work was supported by the Science and Technology Commission of National Natural Science Foundation of China(Nos.21901156,21975148 and 21771124)the Shanghai Municipality(Nos.19JC1412600,18QA1402400 and 18230743400)+4 种基金Z.Feng thanks the startup funding from Oregon State University.The XAS measurements were done at 9-BM of Advanced Photon Source,which is a U.S.Department of Energy(DOE)Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No.DE-AC02-06CH11357.T.Cheng and H.Yang thanks the Natural Science Foundation of Jiangsu Province(Grant No.SBK20190810)the Jiangsu Province High-Level Talents(JNHB-106)the China Postdoctoral Science Foundation(No.2019M660128)the Collaborative Innova-tion Center of Suzhou Nano Science&Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the 111 Project.
文摘Main observation and conclusion Inspired by the nitrogen fixation process on MoFe nitrogenase,asymmetrical coordinated Fe grafted onto 1T MoS_(2) were successfully synthesized.The unique electron-rich structure with asymmetrical coordination made the 1T Fe_(0.1)Mo_(0.9)S_(2) layered material actively react with water and dinitrogen at room temperature and atmosphere pressure.
基金Natural Science Foundation of Hunan Province(2020JJ5757).
文摘As an essential part of DC-Link in the power converter,capacitor plays a crucial role in absorbing ripple current and suppressing ripple voltage.The health and residual service life of the DC-Link capacitor is one of the decisive factors for the safety,stability,and efficiency of the system in which it is located.Aiming at the shortcomings of existing methods,such as low dynamic sensitivity of data update and fluctuation of identification results,a capacitor state identification method based on improved RLS is proposed in this paper.The proposed method is optimized by introducing the forgetting factor algorithm and root means square algorithm to modify the iterative formula and final identification results.Compared with existing methods,this method can identify the capacitor’s current state in real time and accurately.Finally,we successfully verified the accuracy,robustness,and adaptability of the proposed method by a series of experimental tests on a dSPACE platform.