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
Non-precious metal single-atom catalysts(NPM-SACs)with unique electronic structures and coordination environments have gained much attention in electrocatalysis owing to their low cost,high atomic utilization,and high...Non-precious metal single-atom catalysts(NPM-SACs)with unique electronic structures and coordination environments have gained much attention in electrocatalysis owing to their low cost,high atomic utilization,and high performance.NPM-SACs on carbon support(NPM-SACs/CS)are promising because of the carbon substrate with a large surface area,excellent electrical conductivity,and high chemical stability.This review provides an overview of recent developments in NPM-SACs/CS for the electrocatalytic field.First,the state-of-the-art synthesis methods and advanced characterization techniques of NPM-SACs/CS are discussed in detail.Then,the structural adjustment strategy of NPM-SACs/CS for optimizing electrocatalytic performance is introduced concisely.Furthermore,we provide a comprehensive summary of recent advances in developing NPM-SACs/CS for important electrochemical reactions,including carbon dioxide reduction reaction,hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,and nitrogen reduction reaction.In the end,the existing challenges and future opportunities of NPM-SACs/CS in the electrocatalytic field are highlighted.展开更多
Point-of-care(POC)detection of herbicides is of great importance due to their impact on the environment and potential risks to human health.Here,we design a single-atomic site catalyst(SASC)with excellent peroxidase-l...Point-of-care(POC)detection of herbicides is of great importance due to their impact on the environment and potential risks to human health.Here,we design a single-atomic site catalyst(SASC)with excellent peroxidase-like(POD-like)catalytic activity,which enhances the detection performance of corresponding lateral flow immunoassay(LFIA).The iron single-atomic site catalyst(Fe-SASC)is synthesized from hemin-doped ZIF-8,creating active sites that mimic the Fe active center coordination environment of natural enzyme and their functions.Due to its atomically dispersed iron active sites that result in maximum utilization of active metal atoms,the Fe-SASC exhibits superior POD-like activity,which has great potential to replace its natural counterparts.Also,the catalytic mechanism of Fe-SASC is systematically investigated.Utilizing its outstanding catalytic activity,the Fe-SASC is used as label to construct LFIA(Fe-SASC-LFIA)for herbicide detection.The 2,4-dichlorophenoxyacetic acid(2,4-D)is selected as a target here,since it is a commonly used herbicide as well as a biomarker for herbicide exposure evaluation.A linear detection range of 1-250 ng/mL with a low limit of detection(LOD)of 0.82 ng/mL has been achieved.Meanwhile,excellent specificity and selectivity towards 2,4-D have been obtained.The outstanding detection performance of the Fe-SASC-LFIA has also been demonstrated in the detection of human urine samples,indicating the practicability of this POC detection platform for analyzing the 2,4-D exposure level of a person.We believe this proposed Fe-SASC-LFIA has potential as a portable,rapid,and high-sensitive POC detection strategy for pesticide exposure evaluation.展开更多
The Fe–N–C material is a promising non-noblemetal electrocatalyst for oxygen reduction reaction(ORR).Further improvement on the ORR activity is highly desired in order to replace Pt/C in acidic media.Herein,we devel...The Fe–N–C material is a promising non-noblemetal electrocatalyst for oxygen reduction reaction(ORR).Further improvement on the ORR activity is highly desired in order to replace Pt/C in acidic media.Herein,we developed a new-type of single-atom Fe–N–C electrocatalyst,in which Fe–Nxactive sites were modified by P atoms.The half-wave potential of the optimized material reached 0.858 V,which is 23 mV higher than that of the pristine one in a 0.1 mol L-1 HClO4 solution.Density functional theory(DFT)calculations revealed that P-doping can reduce the thermodynamic overpotential of the rate determining step and consequently improve the ORR activity.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
The increasingly severe energy crisis has strengthened the determination to develop environmentally friendly energy.And hydrogen has emerged as a candi-date for clean energy.Among many hydrogen generation methods,bioh...The increasingly severe energy crisis has strengthened the determination to develop environmentally friendly energy.And hydrogen has emerged as a candi-date for clean energy.Among many hydrogen generation methods,biohydrogen stands out due to its environmental sustainability,simple operating environ-ment,and cost advantages.This review focuses on the rational design of catalysts for fermentative hydrogen production.The principles of microbial dark fermen-tation and photo-fermentation are elucidated exhaustively.Various strategies to increase the efficiency of fermentative hydrogen production are summa-rized,and some recent representative works from microbial dark fermentation and photo-fermentation are described.Meanwhile,perspectives and discussions on the rational design of catalysts for fermentative hydrogen production are provided.展开更多
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support from the China Postdoctoral Science Foundation(2022M711553).Y.W.would like to acknowledge the support from the National Natural Science Foundation of China(22171132)the Innovation Fund from Nanjing University(020514913419)+5 种基金the Program for Innovative Talents and Entrepreneurs in Jiangsu(020513006012 and 020513006014),and the National Key R&D Program of China(2002YFB3607000).W.Z.would like to acknowledge the support from the National Natural Science Foundation of China(22176086)Natural Science Foundation of Jiangsu Province(BK20210189)State Key Laboratory of Pollution Control and Resource Reuse(PCRR-ZZ-202106)the Fundamental Research Funds for the Central Universities(021114380183,021114380189 and 021114380199)the Research Funds from the Nanjing Science and Technology Innovation Project for Chinese Scholars Studying Abroad(13006003)the Research Funds from Frontiers Science Center for Critical Earth Material Cycling of Nanjing University,and Research Funds for Jiangsu Distinguished Professor.Y.L.would like to thank the support from the Washington State University startup fund.
文摘Non-precious metal single-atom catalysts(NPM-SACs)with unique electronic structures and coordination environments have gained much attention in electrocatalysis owing to their low cost,high atomic utilization,and high performance.NPM-SACs on carbon support(NPM-SACs/CS)are promising because of the carbon substrate with a large surface area,excellent electrical conductivity,and high chemical stability.This review provides an overview of recent developments in NPM-SACs/CS for the electrocatalytic field.First,the state-of-the-art synthesis methods and advanced characterization techniques of NPM-SACs/CS are discussed in detail.Then,the structural adjustment strategy of NPM-SACs/CS for optimizing electrocatalytic performance is introduced concisely.Furthermore,we provide a comprehensive summary of recent advances in developing NPM-SACs/CS for important electrochemical reactions,including carbon dioxide reduction reaction,hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,and nitrogen reduction reaction.In the end,the existing challenges and future opportunities of NPM-SACs/CS in the electrocatalytic field are highlighted.
基金support from the National Institute of Environmental Health Sciences of the US National Institutes of Health(Award Number 1R43ES031885-01)。
文摘Point-of-care(POC)detection of herbicides is of great importance due to their impact on the environment and potential risks to human health.Here,we design a single-atomic site catalyst(SASC)with excellent peroxidase-like(POD-like)catalytic activity,which enhances the detection performance of corresponding lateral flow immunoassay(LFIA).The iron single-atomic site catalyst(Fe-SASC)is synthesized from hemin-doped ZIF-8,creating active sites that mimic the Fe active center coordination environment of natural enzyme and their functions.Due to its atomically dispersed iron active sites that result in maximum utilization of active metal atoms,the Fe-SASC exhibits superior POD-like activity,which has great potential to replace its natural counterparts.Also,the catalytic mechanism of Fe-SASC is systematically investigated.Utilizing its outstanding catalytic activity,the Fe-SASC is used as label to construct LFIA(Fe-SASC-LFIA)for herbicide detection.The 2,4-dichlorophenoxyacetic acid(2,4-D)is selected as a target here,since it is a commonly used herbicide as well as a biomarker for herbicide exposure evaluation.A linear detection range of 1-250 ng/mL with a low limit of detection(LOD)of 0.82 ng/mL has been achieved.Meanwhile,excellent specificity and selectivity towards 2,4-D have been obtained.The outstanding detection performance of the Fe-SASC-LFIA has also been demonstrated in the detection of human urine samples,indicating the practicability of this POC detection platform for analyzing the 2,4-D exposure level of a person.We believe this proposed Fe-SASC-LFIA has potential as a portable,rapid,and high-sensitive POC detection strategy for pesticide exposure evaluation.
基金This work was supported by the National Key R&D Program of China(2017YFB0102900)the Research Grant Council(N一HKUST610/17)of Hong Kong Special Administrative Region.It used resources of the Advanced Photon Source,Office of Science user facilities,supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences(DE-AC02-06CH11357).
文摘The Fe–N–C material is a promising non-noblemetal electrocatalyst for oxygen reduction reaction(ORR).Further improvement on the ORR activity is highly desired in order to replace Pt/C in acidic media.Herein,we developed a new-type of single-atom Fe–N–C electrocatalyst,in which Fe–Nxactive sites were modified by P atoms.The half-wave potential of the optimized material reached 0.858 V,which is 23 mV higher than that of the pristine one in a 0.1 mol L-1 HClO4 solution.Density functional theory(DFT)calculations revealed that P-doping can reduce the thermodynamic overpotential of the rate determining step and consequently improve the ORR activity.
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W.Z.would like to acknowledge the support from National Natural Science Foundation of China(grant number:22176086)Natural Science Foundation of Jiangsu Province(grant number:BK20210189)+2 种基金State Key laboratory of Pollution Control and Resource Reuse(grant number:PCRR-ZZ-202106)the Fundamental Research Funds for the Central Universities(grant number:021114380183 and 021114380189)the Research Funds from Frontiers Science Center for Critical Earth Material Cycling of Nanjing University,and Research Funds for Jiangsu Distinguished Professor.Y.L.would like to acknowledge the start-up fund from Washington State University.
文摘The increasingly severe energy crisis has strengthened the determination to develop environmentally friendly energy.And hydrogen has emerged as a candi-date for clean energy.Among many hydrogen generation methods,biohydrogen stands out due to its environmental sustainability,simple operating environ-ment,and cost advantages.This review focuses on the rational design of catalysts for fermentative hydrogen production.The principles of microbial dark fermen-tation and photo-fermentation are elucidated exhaustively.Various strategies to increase the efficiency of fermentative hydrogen production are summa-rized,and some recent representative works from microbial dark fermentation and photo-fermentation are described.Meanwhile,perspectives and discussions on the rational design of catalysts for fermentative hydrogen production are provided.