Molecular engineering has demonstrated significant potential in modulating the crystallization and interfacial defect passivation of perovskite films.However,the deprotonation of conventional organic ammonium under li...Molecular engineering has demonstrated significant potential in modulating the crystallization and interfacial defect passivation of perovskite films.However,the deprotonation of conventional organic ammonium under light or thermal stress compromises the long-term operational stability of perovskite solar cells(PSCs).Here,we designed two multifunctional deprotonation-resistant cycloalkyl amidines with different heteroatoms,tetrahydro-2H-pyran-4-carboximidamide hydroiodide(TPCAI)and tetrahydro-2H-t hiopyran-4-carboximidamide hydroiodide(TTCAI),which were used to precisely regulate the crystallization process and interfacial properties of perovskite films.The larger dipole moment and enhanced electronic properties of sulfur-substituted TTCAI than TPCAI strengthen its interaction with the perovskite lattice.This interaction markedly slows down the crystallization rate,promotes preferential growth along the(100)crystal plane,reduces defect density,and effectively suppresses non-radiative recombination.TTCAI meanwhile construction of passivation layers on the surface and grain boundaries of the perovskite film through multiple hydrogen-bond interactions,passivates grain boundary defects,which significantly improves the film's environmental stability.Consequently,the TTCAI-modified device achieved a high efficiency of 25.58%,and the unencapsulated device retained 92%of its initial efficiency after 1200 h of storage at 65℃ under air(RH 30–65%).This study provides new insights into the rational design of multifunctional amidine ligands toward achieving efficient and stable PSCs.展开更多
The field of nanomedicine has been revolutionized by the concept of immunogenic cell death(ICD)-enhanced cancer therapy,which holds immense promise for the efficient treatment of cancer.However,precise delivery of ICD...The field of nanomedicine has been revolutionized by the concept of immunogenic cell death(ICD)-enhanced cancer therapy,which holds immense promise for the efficient treatment of cancer.However,precise delivery of ICD inducer is severely hindered by complex biological barriers.How to design and build intelligent nanoplatform for adaptive and dynamic cancer therapy remains a big challenge.Herein,this article presents the design and preparation of CD44-targeting and ZIF-8 gated gold nanocage(Au@ZH) for programmed delivery of the 1,2-diaminocyclohexane-Pt(Ⅱ)(DACHPt) as ICD inducer.After actively targeting the CD44 on the surface of 4T1 tumor cell,this Pt-Au@ZH can be effectively endocytosed by the 4T1 cell and release the DACHPt in tumor acidic environment,resulting in ICD effect and superior antitumor efficacy both in vitro and in vivo in the presence of mild 808 nm laser irradiation.By integration of internal and external stimuli intelligently,this programmed nanoplatform is poised to become a cornerstone in the pursuit of effective and targeted cancer therapy in the foreseeable future.展开更多
As the main component of the aircraft leading edge,the radome is often the first to be hit by raindrops and cause structural damage when passing through a rain field.Rain resistant coating is usually applied to ensure...As the main component of the aircraft leading edge,the radome is often the first to be hit by raindrops and cause structural damage when passing through a rain field.Rain resistant coating is usually applied to ensure the performance protection requirements.In order to clarify the rain erosion damage mechanism of radome coating and explore the influencing factors and mechanisms of coating material damage under different jet impact conditions,impact tests were conducted on three types of skin coating samples,and the damage mode was observed through electron microscopy characterization.The experimental results show that the typical morphology of rain erosion damage is annular surface peeling damage.The damage area and volume of the three coating samples increase with the continuous increase of raindrop impact velocity.The threshold velocity for initial damage to the coating is about 360 m/s;under the influence of the velocity component,the reduction in impact angle leads to a gradual reduction in the degree of damage to the sample.ABAQUS finite element simulation software was used to establish a constitutive model for coating rain erosion simulation and obtain the propagation law of stress waves during the impact process.The simulation results show that at the 75°impact angle,the jet impacts the surface of the specimen at different velocities,and as the impact velocity increases,the Mises equivalent stress on the surface shows an increasing trend,which is one of the main factors causing damage with increasing velocity.The effectiveness,rain erosion damage mode,and influencing mechanism of the model were verified based on the test results;the dynamic failure mechanism of the sample was further studied,and the stress propagation process at different impact angles was compared,revealing the influence mechanism and damage law of the impact angle on the high-speed raindrop impact of the material.展开更多
Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer ...Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer from insufficient hole transport capability,which hinders the overall activity.The present study demonstrates that a simple photoetching strategy is able to introduce gradient distributed oxygen vacancies(GO_(V))in the thick FeOOH layer and significantly enhances the photogenerated holes transport dynamics.The incorporation of GO_(V)within FeOOH not only realizes the“relay transport”of photogenerated hole through the progressive upward shift of the valence band in the spatial distribution,but also provides abundant oxidation active sites by efficient hole trapping.These improvements effectively improve the oxygen evolution reaction(OER)activities and mitigate photocorrosion by the instantaneous hole extraction.Consequently,the FeOOH-GO_(V)layer enables the BVO/FeOOH-GO_(V)photoanode to achieve an impressive photocurrent density of 5.37 mA cm^(-2)and a robust operational stability up to 160 h at 1.23 VRHE,setting new benchmarks for current density and stability in FeOOH-based BVO photoanodes.This work provides an effective avenue to optimize OER cocatalysts for constructing highly efficient and stable photoelectrochemical water splitting devices.展开更多
Pb-Sn mixed perovskite solar cells(PSCs)are crucial components for realizing efficient all-perovskite tandem devices.However,their efficiency and stability are severely limited by oxidative degradation(Sn^(4+)formatio...Pb-Sn mixed perovskite solar cells(PSCs)are crucial components for realizing efficient all-perovskite tandem devices.However,their efficiency and stability are severely limited by oxidative degradation(Sn^(4+)formation)and metallic defects(Sn^(0)/Pb^(0)).In addition,the rapid and uncontrolled Sn^(2+)nucleation kinetics result in nonuniform crystallization.Herein,we introduce a natural redox shuttle glutathione(GSH)in Pb-Sn mixed PSCs,achieving regenerable antioxidation and crystallization regulation simultaneously.The reversible redox reactions between GSH and glutathione disulfide(GSSG)enable the self-healing of Sn^(4+)and Sn^(0)/Pb^(0)impurities,creating a regenerable antioxidation protective shell at the perovskite interfaces.Meanwhile,the strong coordination between GSH and perovskite regulates the crystallization process,optimizing the nucleation and crystallization kinetics.Furthermore,the GSH incorporation creates a high-quality charge separation junction at the perovskite/hole transport layer,facilitating carrier separation and extraction.The optimized Pb-Sn PSCs exhibit impressive power conversion efficiencies(PCEs)of up to 23.71%.The champion all-perovskite tandem PSCs with GSH achieve a PCE of 28.49%and retain 90%of the initial PCE after 560 h of continuous illumination.This work establishes a new nature-inspired redox shuttling strategy and elucidates its working mechanism,advancing the development of efficient and stable all-perovskite tandem solar cells.展开更多
基金supported by the National Natural Science Foundation of China(22471218)Shaanxi Fundamental Science Research Project for Chemistry&Biology(22JHQ002)+3 种基金Program for Young Talents of Shaanxi Province(5113190023)the Natural Science Foundation of Shaanxi Province(2025JC-YBMS-147 and2024JC-ZDXM-08)the Natural Science Foundation of Zhejiang Province(LY24B010002)the Natural Science Foundation of Guangdong Province(2025A1515012305)。
文摘Molecular engineering has demonstrated significant potential in modulating the crystallization and interfacial defect passivation of perovskite films.However,the deprotonation of conventional organic ammonium under light or thermal stress compromises the long-term operational stability of perovskite solar cells(PSCs).Here,we designed two multifunctional deprotonation-resistant cycloalkyl amidines with different heteroatoms,tetrahydro-2H-pyran-4-carboximidamide hydroiodide(TPCAI)and tetrahydro-2H-t hiopyran-4-carboximidamide hydroiodide(TTCAI),which were used to precisely regulate the crystallization process and interfacial properties of perovskite films.The larger dipole moment and enhanced electronic properties of sulfur-substituted TTCAI than TPCAI strengthen its interaction with the perovskite lattice.This interaction markedly slows down the crystallization rate,promotes preferential growth along the(100)crystal plane,reduces defect density,and effectively suppresses non-radiative recombination.TTCAI meanwhile construction of passivation layers on the surface and grain boundaries of the perovskite film through multiple hydrogen-bond interactions,passivates grain boundary defects,which significantly improves the film's environmental stability.Consequently,the TTCAI-modified device achieved a high efficiency of 25.58%,and the unencapsulated device retained 92%of its initial efficiency after 1200 h of storage at 65℃ under air(RH 30–65%).This study provides new insights into the rational design of multifunctional amidine ligands toward achieving efficient and stable PSCs.
基金financially supported by the Natural Science Foundation of Jiangsu Province (No.BK20200709)the Natural Science Foundation of China (Nos.62288102,32201127 and 82270113)+2 种基金the Natural Science Foundation of Guangdong Province (No.2023A1515011386)the Natural Science Foundation of the Jiangsu Higher Education Institutes (No.20KJB430031)the startup fund from Nanjing Tech University,and Disciplinary Fund of School of Pharmaceutical Sciences (2024)。
文摘The field of nanomedicine has been revolutionized by the concept of immunogenic cell death(ICD)-enhanced cancer therapy,which holds immense promise for the efficient treatment of cancer.However,precise delivery of ICD inducer is severely hindered by complex biological barriers.How to design and build intelligent nanoplatform for adaptive and dynamic cancer therapy remains a big challenge.Herein,this article presents the design and preparation of CD44-targeting and ZIF-8 gated gold nanocage(Au@ZH) for programmed delivery of the 1,2-diaminocyclohexane-Pt(Ⅱ)(DACHPt) as ICD inducer.After actively targeting the CD44 on the surface of 4T1 tumor cell,this Pt-Au@ZH can be effectively endocytosed by the 4T1 cell and release the DACHPt in tumor acidic environment,resulting in ICD effect and superior antitumor efficacy both in vitro and in vivo in the presence of mild 808 nm laser irradiation.By integration of internal and external stimuli intelligently,this programmed nanoplatform is poised to become a cornerstone in the pursuit of effective and targeted cancer therapy in the foreseeable future.
基金supported by the National Natural Science Foundation of China(Nos.12261131505,U2241274)the Russian Science Fund(No.23-49-00133)+3 种基金the Aeronautical Science Foundation of China(No.20240002053002)the Natural Science Basic Research Program of Shaanxi,China(No.2025JC-YBMS-005)the Key Research and Development Program of Shaanxi,China(No.2024GX-YBXM-037)the Basic Research Programs of Taicang,China(No.TC2024JC10)。
文摘As the main component of the aircraft leading edge,the radome is often the first to be hit by raindrops and cause structural damage when passing through a rain field.Rain resistant coating is usually applied to ensure the performance protection requirements.In order to clarify the rain erosion damage mechanism of radome coating and explore the influencing factors and mechanisms of coating material damage under different jet impact conditions,impact tests were conducted on three types of skin coating samples,and the damage mode was observed through electron microscopy characterization.The experimental results show that the typical morphology of rain erosion damage is annular surface peeling damage.The damage area and volume of the three coating samples increase with the continuous increase of raindrop impact velocity.The threshold velocity for initial damage to the coating is about 360 m/s;under the influence of the velocity component,the reduction in impact angle leads to a gradual reduction in the degree of damage to the sample.ABAQUS finite element simulation software was used to establish a constitutive model for coating rain erosion simulation and obtain the propagation law of stress waves during the impact process.The simulation results show that at the 75°impact angle,the jet impacts the surface of the specimen at different velocities,and as the impact velocity increases,the Mises equivalent stress on the surface shows an increasing trend,which is one of the main factors causing damage with increasing velocity.The effectiveness,rain erosion damage mode,and influencing mechanism of the model were verified based on the test results;the dynamic failure mechanism of the sample was further studied,and the stress propagation process at different impact angles was compared,revealing the influence mechanism and damage law of the impact angle on the high-speed raindrop impact of the material.
基金supported by the State Key Laboratory of Solidification Processing in NWPU(SKLSP202407)the National Natural Science Foundation of China(52402130)+2 种基金the Natural Science Basis Research Plan in Shaanxi Province of China(2024JC-YBQN-0384)the Shaanxi Science and Technology Innovation Team(2023-CX-TD-44)the National Natural Science Foundation of China(52301015).
文摘Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer from insufficient hole transport capability,which hinders the overall activity.The present study demonstrates that a simple photoetching strategy is able to introduce gradient distributed oxygen vacancies(GO_(V))in the thick FeOOH layer and significantly enhances the photogenerated holes transport dynamics.The incorporation of GO_(V)within FeOOH not only realizes the“relay transport”of photogenerated hole through the progressive upward shift of the valence band in the spatial distribution,but also provides abundant oxidation active sites by efficient hole trapping.These improvements effectively improve the oxygen evolution reaction(OER)activities and mitigate photocorrosion by the instantaneous hole extraction.Consequently,the FeOOH-GO_(V)layer enables the BVO/FeOOH-GO_(V)photoanode to achieve an impressive photocurrent density of 5.37 mA cm^(-2)and a robust operational stability up to 160 h at 1.23 VRHE,setting new benchmarks for current density and stability in FeOOH-based BVO photoanodes.This work provides an effective avenue to optimize OER cocatalysts for constructing highly efficient and stable photoelectrochemical water splitting devices.
基金supported by Guangdong Basic and Applied Basic Research Foundation(2025A1515011362)the National Natural Science Foundation of China(52102304,52172238)Open Project of Shaanxi Laboratory of Aerospace Power(2021SXSYS-01-03).
文摘Pb-Sn mixed perovskite solar cells(PSCs)are crucial components for realizing efficient all-perovskite tandem devices.However,their efficiency and stability are severely limited by oxidative degradation(Sn^(4+)formation)and metallic defects(Sn^(0)/Pb^(0)).In addition,the rapid and uncontrolled Sn^(2+)nucleation kinetics result in nonuniform crystallization.Herein,we introduce a natural redox shuttle glutathione(GSH)in Pb-Sn mixed PSCs,achieving regenerable antioxidation and crystallization regulation simultaneously.The reversible redox reactions between GSH and glutathione disulfide(GSSG)enable the self-healing of Sn^(4+)and Sn^(0)/Pb^(0)impurities,creating a regenerable antioxidation protective shell at the perovskite interfaces.Meanwhile,the strong coordination between GSH and perovskite regulates the crystallization process,optimizing the nucleation and crystallization kinetics.Furthermore,the GSH incorporation creates a high-quality charge separation junction at the perovskite/hole transport layer,facilitating carrier separation and extraction.The optimized Pb-Sn PSCs exhibit impressive power conversion efficiencies(PCEs)of up to 23.71%.The champion all-perovskite tandem PSCs with GSH achieve a PCE of 28.49%and retain 90%of the initial PCE after 560 h of continuous illumination.This work establishes a new nature-inspired redox shuttling strategy and elucidates its working mechanism,advancing the development of efficient and stable all-perovskite tandem solar cells.
