Beyond conventional electrocatalyst engineering,recent studies have demonstrated the effectiveness of manipulating the local reaction environment to enhance the performance of electrocatalytic reactions.The general pr...Beyond conventional electrocatalyst engineering,recent studies have demonstrated the effectiveness of manipulating the local reaction environment to enhance the performance of electrocatalytic reactions.The general principles and strategies of local environmental engineering for different electrocatalytic processes have been extensively investigated.This perspective critically appraises the recent advancements in local reaction environment engineering for water activation,aiming to provide a comprehensive assessment of this emerging field.展开更多
Conventional proton exchange membrane(PEM)electrolysis technology relies on ultrapure water,as cationic impurities(such as Na^(+),Ca^(2+) and Fe^(3+))can occupy H+transport sites in the membrane[1],leading to a sharp ...Conventional proton exchange membrane(PEM)electrolysis technology relies on ultrapure water,as cationic impurities(such as Na^(+),Ca^(2+) and Fe^(3+))can occupy H+transport sites in the membrane[1],leading to a sharp rise in cathode pH,catalyst deactivation,and membrane degradation[2].This forces the system to be equipped with complex water purification equipment and even necessitates the replacement of membrane electrode assemblies(MEAs),increasing the levelized cost of hydrogen(LCOH)[3].To address this,Tao Ling's group recently proposed a"local pH regulation"strategy in Nature Energy[4].展开更多
Design of electrochemical active boron(B)site at solid materials to understand the relationships between the localized structure,charge state at the B site and electrocatalytic activity plays a crucial role in boostin...Design of electrochemical active boron(B)site at solid materials to understand the relationships between the localized structure,charge state at the B site and electrocatalytic activity plays a crucial role in boosting the green electrochemical synthesis of hydrogen peroxide(H_(2)O_(2))via two-electron oxygen reduction(2eORR)pathway.Herein,we demonstrate a carbon(C)and nitrogen(N)localized bonding microenvironment to modulate the charge state of B site at the boron-carbon nitride solid(BCNs)to realize the efficient selective electrocatalytic H_(2)O_(2)production.The localized chemical structure of N-B-N,N-B-C and C-B-C bonds at B site can be regulated through solid-state reaction between boron nitride(BN)and porous carbon(C)at variable temperatures.The optimized BCN-1100 achieves an outstanding H_(2)O_(2)selectivity of 89%and electron transfer number of 2.2(at 0.55 V vs.RHE),with the production of 10.55mmol/L during 2.5 h and the catalytic stability duration for 15000 cycles.Further first-principles calculations identified the dependency of localized bonding microenvironment on the OOH~*adsorption energies and relevant charge states at the boron site.The localized structure of B site with BNC_(2)-Gr configuration is predicted to be the highest 2eORR activity.展开更多
Electrochemical carbon dioxide reduction reaction(CO_(2)RR)converts CO_(2) into valuable chemicals by consuming renewable electricity at mild conditions,making it a promising approach to achieving carbon neutrality.Ho...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)converts CO_(2) into valuable chemicals by consuming renewable electricity at mild conditions,making it a promising approach to achieving carbon neutrality.However,the reaction of CO_(2) with hydroxide ions to form carbonates leads to low carbon utilization and energy efficiency in near-neutral or alkaline CO_(2)RR.The high concentration of protons in acidic media can effectively mitigate carbonate formation and deposition,thereby significantly minimizing carbon loss and energy consumption.Unfortunately,hydrogen evolution reaction(HER)is more kinetically favorable than CO_(2)RR in acidic media.Herein,we comprehensively overview recent progress in acidic CO_(2)RR and propose two strategies derived from the competing reaction pathways of HER and CO_(2)RR:one focuses on regulating the H+mass transport,while the other aims to modulate the intrinsic kinetic activity of CO_(2)RR.The two strategies are designed to compete for the limited active sites on the catalyst surface,inhibit side reactions,and enhance the activity and selectivity of CO_(2)RR.The representative approaches include modulating the interface electric field,constructing a local alkaline environment,and regulating competing adsorption sites.Finally,we also review the technical challenges and future perspectives of acidic CO_(2)RR coupled with membrane electrode assemblies(MEAs).展开更多
While chemo-immunotherapy has been established as the frontline therapeutic regimen for extensive-stage small cell lung cancer(ES-SCLC),durable responses persist predominantly in a minor population of patients.This un...While chemo-immunotherapy has been established as the frontline therapeutic regimen for extensive-stage small cell lung cancer(ES-SCLC),durable responses persist predominantly in a minor population of patients.This underscores critical need to elucidate underlying local tumor microenvironment and systematic immune profles for biomarker discovery.In this phase ll trial(ChiCTR2000038354),the efficacy,safety,and immune-genomic signatures of sintilimab(anti-PD-1 antibody)synergized with chemotherapy as first-line regimen for ES-SCLC were evaluated.The regimen demonstrated a median progression-free survival(PFS)of 6.9 months and median overall survival of 17.1 months,accompanied by a 12-month PFS rate of 16.9%,fulflling the primary endpoint.Manageable grade 3 or 4 treatment-related adverse events developed in 27.3%(12/44)of patients.The exploratory study indicated a higher infiltration of CD4^(+)/CD8^(+)CXCR5^(+)T follicle helper cell,CD8^(+)CD103^(+)tissue-resident memory T cells,and B cells in tumor tissue,associated with better response and prognosis.The study also indicated the presence of tumor macrophages(CD68^(+)CD163^(+)CSF1R^(+)SIGLEC5^(+))associated with immunotherapy resistance.Higher levels of monocyte-dendritic cells in pre-treatment peripheral blood mononuclear cells were found in durable clinical benefit group.Also,higher CD83,CD244,IL-12,and CD70,which are hallmarks of dendritic cells and activated T cells,were discovered by plasma proteomics to be connected with enhanced outcomes,while chemoattractant of macrophage,CSF-1,CCL3,CCL4,and IL-8,were found to predict a worse prognosis.Furthermore,a multimodal model was constructed and validated for stratifying ES-SCLC into high or low risk to predict the immunotherapy efficacy.This study sheds light on harnessing local and systematic immune profiles to better stratify patients with ES-SCLC for immunotherapy and putative combinational treatment.展开更多
Alkaline seawater electrolysis for hydrogen production powered by clean energy is increasingly driving the development of a low-carbon economy.However,the limited proton availability in the electrolyte leads to sluggi...Alkaline seawater electrolysis for hydrogen production powered by clean energy is increasingly driving the development of a low-carbon economy.However,the limited proton availability in the electrolyte leads to sluggish cathodic reaction kinetics and elevates energy consumption,which hinders its large-scale application.Herein,low Pt loaded NiCo phosphate-coated NiCoP nanoneedle arrays on Ni foam(Pt@NCPi@NCP/NF)using a spontaneous redox strategy is developed for efficient and durable electrocatalytic hydrogen production from alkaline seawater.In situ Raman spectroscopy confirms that a large number of hydrated hydrogen ion intermediates are generated on the surface of Pt@NCPi@NCP/NF during the hydrogen evolution reaction(HER)process,which successfully constructs a localized acidic microenvironment.Concurrently,the surface Pi layer functions as a proton buffer layer,effectively regulating proton supply to enhance the utilization efficiency of active sites.As a result,the catalyst exhibits excellent HER kinetics under alkaline conditions with a Tafel slope of only 39.65 mV·dec^(-1)and a low overpotential of 136 mV to reach 1000 mA·cm^(-2).展开更多
Micro/nanomotors(MNMs)have recently emerged as highly promising drug delivery vehicles,showing great potential for biomedical applications.MNMs are typically classified based on their driving mechanisms,and one notabl...Micro/nanomotors(MNMs)have recently emerged as highly promising drug delivery vehicles,showing great potential for biomedical applications.MNMs are typically classified based on their driving mechanisms,and one notable category is gas-driven MNMs,which are self-propelled at the micro/nano scale by gases generated through chemical reactions.These motors can effectively overcome various physiological barriers by utilizing unique physiological actions and driving forces in vivo,gas-driven MNMs offer significant advantages in treating diseases such as tumors and thrombosis.This review first explores the underlying mechanisms of gas-driven MNMs,then discusses their recent applications in overcoming physiological barriers.Finally,it analyses their future prospects and advantages,aiming to inspire further research and accelerate clinical translation in the biomedical field.展开更多
基金funded by the National Natural Science Foundation of China(22208331)the Science and Technology Innovation Fund of Wuhan Textile University(243001)+3 种基金Department of Science and Technology of Hubei Province(2021CSA076)the National Key Research and Development Program of China(2022YFE0138900)the National Natural Science Foundation of China(21972017)the"Scientific and Technical Innovation Action Plan"Basic Research Field of Shanghai Science and Technology Committee(19JC1410500).
文摘Beyond conventional electrocatalyst engineering,recent studies have demonstrated the effectiveness of manipulating the local reaction environment to enhance the performance of electrocatalytic reactions.The general principles and strategies of local environmental engineering for different electrocatalytic processes have been extensively investigated.This perspective critically appraises the recent advancements in local reaction environment engineering for water activation,aiming to provide a comprehensive assessment of this emerging field.
基金the Natural Science Foundation of Guangxi,China(No.2021GXNSFBA220058)the National Natural Science Foundation of China(Nos.22272036, 22362008)Guangxi Normal University Research Grant,China(No.2022TD).
文摘Conventional proton exchange membrane(PEM)electrolysis technology relies on ultrapure water,as cationic impurities(such as Na^(+),Ca^(2+) and Fe^(3+))can occupy H+transport sites in the membrane[1],leading to a sharp rise in cathode pH,catalyst deactivation,and membrane degradation[2].This forces the system to be equipped with complex water purification equipment and even necessitates the replacement of membrane electrode assemblies(MEAs),increasing the levelized cost of hydrogen(LCOH)[3].To address this,Tao Ling's group recently proposed a"local pH regulation"strategy in Nature Energy[4].
基金financially supported by the National Natural Science Foundation of China(Nos.22161036,11904187,21961024 and 21961025)Natural Science Foundation of Inner Mongolia(Nos.2018JQ05 and 2019BS02007)+2 种基金Incentive Funding from Nano Innovation Institute(NII)of Inner Mongolia Minzu Universitythe Inner Mongolia Autonomous Region Funding Project for Science&Technology Achievement Transformation(Nos.CGZH2018156 and 2019GG261)Doctoral Scientific Research Foundation of Inner Mongolia Minzu University(Nos.BS437 and BS480)。
文摘Design of electrochemical active boron(B)site at solid materials to understand the relationships between the localized structure,charge state at the B site and electrocatalytic activity plays a crucial role in boosting the green electrochemical synthesis of hydrogen peroxide(H_(2)O_(2))via two-electron oxygen reduction(2eORR)pathway.Herein,we demonstrate a carbon(C)and nitrogen(N)localized bonding microenvironment to modulate the charge state of B site at the boron-carbon nitride solid(BCNs)to realize the efficient selective electrocatalytic H_(2)O_(2)production.The localized chemical structure of N-B-N,N-B-C and C-B-C bonds at B site can be regulated through solid-state reaction between boron nitride(BN)and porous carbon(C)at variable temperatures.The optimized BCN-1100 achieves an outstanding H_(2)O_(2)selectivity of 89%and electron transfer number of 2.2(at 0.55 V vs.RHE),with the production of 10.55mmol/L during 2.5 h and the catalytic stability duration for 15000 cycles.Further first-principles calculations identified the dependency of localized bonding microenvironment on the OOH~*adsorption energies and relevant charge states at the boron site.The localized structure of B site with BNC_(2)-Gr configuration is predicted to be the highest 2eORR activity.
基金supported by the National Natural Science Foundation of China(52301259 and 22208019)the Research Fund Program for Young Scholars of Beijing Institute of Technology。
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)converts CO_(2) into valuable chemicals by consuming renewable electricity at mild conditions,making it a promising approach to achieving carbon neutrality.However,the reaction of CO_(2) with hydroxide ions to form carbonates leads to low carbon utilization and energy efficiency in near-neutral or alkaline CO_(2)RR.The high concentration of protons in acidic media can effectively mitigate carbonate formation and deposition,thereby significantly minimizing carbon loss and energy consumption.Unfortunately,hydrogen evolution reaction(HER)is more kinetically favorable than CO_(2)RR in acidic media.Herein,we comprehensively overview recent progress in acidic CO_(2)RR and propose two strategies derived from the competing reaction pathways of HER and CO_(2)RR:one focuses on regulating the H+mass transport,while the other aims to modulate the intrinsic kinetic activity of CO_(2)RR.The two strategies are designed to compete for the limited active sites on the catalyst surface,inhibit side reactions,and enhance the activity and selectivity of CO_(2)RR.The representative approaches include modulating the interface electric field,constructing a local alkaline environment,and regulating competing adsorption sites.Finally,we also review the technical challenges and future perspectives of acidic CO_(2)RR coupled with membrane electrode assemblies(MEAs).
基金funded by the Clinical Research Foundation of Shanghai Pulmonary Hospital(FKLY20013)National Key R&D Program of China(grant number 2023YFC2508604,2023YFC2508605)+2 种基金Tongji University Medicine-X Interdisciplinary Research Initiative(2025-0554-ZD-08)"Young Eagle Soaring"Talent Project of Shanghai Pulmonary Hospital(Fkcy2408)Innovent Biologics,Inc and Amoy Diagnostics Co.,Ltd.The IRB of Shanghai Pulmonary Hospital(L20-411-1)approved the protocol,all patients provided written informed consent.
文摘While chemo-immunotherapy has been established as the frontline therapeutic regimen for extensive-stage small cell lung cancer(ES-SCLC),durable responses persist predominantly in a minor population of patients.This underscores critical need to elucidate underlying local tumor microenvironment and systematic immune profles for biomarker discovery.In this phase ll trial(ChiCTR2000038354),the efficacy,safety,and immune-genomic signatures of sintilimab(anti-PD-1 antibody)synergized with chemotherapy as first-line regimen for ES-SCLC were evaluated.The regimen demonstrated a median progression-free survival(PFS)of 6.9 months and median overall survival of 17.1 months,accompanied by a 12-month PFS rate of 16.9%,fulflling the primary endpoint.Manageable grade 3 or 4 treatment-related adverse events developed in 27.3%(12/44)of patients.The exploratory study indicated a higher infiltration of CD4^(+)/CD8^(+)CXCR5^(+)T follicle helper cell,CD8^(+)CD103^(+)tissue-resident memory T cells,and B cells in tumor tissue,associated with better response and prognosis.The study also indicated the presence of tumor macrophages(CD68^(+)CD163^(+)CSF1R^(+)SIGLEC5^(+))associated with immunotherapy resistance.Higher levels of monocyte-dendritic cells in pre-treatment peripheral blood mononuclear cells were found in durable clinical benefit group.Also,higher CD83,CD244,IL-12,and CD70,which are hallmarks of dendritic cells and activated T cells,were discovered by plasma proteomics to be connected with enhanced outcomes,while chemoattractant of macrophage,CSF-1,CCL3,CCL4,and IL-8,were found to predict a worse prognosis.Furthermore,a multimodal model was constructed and validated for stratifying ES-SCLC into high or low risk to predict the immunotherapy efficacy.This study sheds light on harnessing local and systematic immune profiles to better stratify patients with ES-SCLC for immunotherapy and putative combinational treatment.
文摘Alkaline seawater electrolysis for hydrogen production powered by clean energy is increasingly driving the development of a low-carbon economy.However,the limited proton availability in the electrolyte leads to sluggish cathodic reaction kinetics and elevates energy consumption,which hinders its large-scale application.Herein,low Pt loaded NiCo phosphate-coated NiCoP nanoneedle arrays on Ni foam(Pt@NCPi@NCP/NF)using a spontaneous redox strategy is developed for efficient and durable electrocatalytic hydrogen production from alkaline seawater.In situ Raman spectroscopy confirms that a large number of hydrated hydrogen ion intermediates are generated on the surface of Pt@NCPi@NCP/NF during the hydrogen evolution reaction(HER)process,which successfully constructs a localized acidic microenvironment.Concurrently,the surface Pi layer functions as a proton buffer layer,effectively regulating proton supply to enhance the utilization efficiency of active sites.As a result,the catalyst exhibits excellent HER kinetics under alkaline conditions with a Tafel slope of only 39.65 mV·dec^(-1)and a low overpotential of 136 mV to reach 1000 mA·cm^(-2).
基金supported by the National Natural Science Foundation of China(Nos.82222067,and 82102936)Outstanding Youth Foundation of Henan Province Henan(No.222300420020)+3 种基金China Postdoctoral Science Foundation(No.2023M743232)the Postdoctoral Fellowship Program of CPSF under Grant Number(No.GZB20230676)Scientific and Technological Innovation Talent in Central Plains,Key Projects of Advantageous disciplines in Henan Province(No.222301420011)Scientific and Technological Project of Henan Province(No.242102310450).
文摘Micro/nanomotors(MNMs)have recently emerged as highly promising drug delivery vehicles,showing great potential for biomedical applications.MNMs are typically classified based on their driving mechanisms,and one notable category is gas-driven MNMs,which are self-propelled at the micro/nano scale by gases generated through chemical reactions.These motors can effectively overcome various physiological barriers by utilizing unique physiological actions and driving forces in vivo,gas-driven MNMs offer significant advantages in treating diseases such as tumors and thrombosis.This review first explores the underlying mechanisms of gas-driven MNMs,then discusses their recent applications in overcoming physiological barriers.Finally,it analyses their future prospects and advantages,aiming to inspire further research and accelerate clinical translation in the biomedical field.
