The solution processibility of perovskites provides a costeffective and high-throughput route for fabricating state-of-the-art solar cells.However,the fast kinetics of precursor-to-perovskite transformation is suscept...The solution processibility of perovskites provides a costeffective and high-throughput route for fabricating state-of-the-art solar cells.However,the fast kinetics of precursor-to-perovskite transformation is susceptible to processing conditions,resulting in an uncontrollable variance in device performance.Here,we demonstrate a supramolecule confined approach to reproducibly fabricate perovskite films with an ultrasmooth,electronically homogeneous surface.The assembly of a calixarene capping layer on precursor surface can induce host-vip interactions with solvent molecules to tailor the desolvation kinetics,and initiate the perovskite crystallization from the sharp molecule-precursor interface.These combined effects significantly reduced the spatial variance and extended the processing window of perovskite films.As a result,the standard efficiency deviations of device-to-device and batch-to-batch devices were reduced from 0.64-0.26%to 0.67-0.23%,respectively.In addition,the perovskite films with ultrasmooth top surfaces exhibited photoluminescence quantum yield>10%and surface recombination velocities<100 cm s^(-1)for both interfaces that yielded p-i-n structured solar cells with power conversion efficiency over 25%.展开更多
Noble metal-based intermetallics are promising electrocatalysts for sustainable energy conversion and consumption processes.High-temperature pyrolysis(>500°C)methods are used to control their crystalline order...Noble metal-based intermetallics are promising electrocatalysts for sustainable energy conversion and consumption processes.High-temperature pyrolysis(>500°C)methods are used to control their crystalline orderings,critical to their electrocatalytic activity and durability.However,the high temperature would cause severe aggregation,resulting in a low catalytic active surface area.Significant research efforts have been devoted to addressing this issue.This short review summarizes recent research progress on synthesizing noble metal-based intermetallic electrocatalysts by space-confined pyrolysis.We focus on three strategies:isolation in pores,coverture by shells,and immobilization by salts.The advantages and existing problems of different methods are highlighted.Last,important issues to be addressed in future research are also discussed.We hope that this article will stimulate future research to develop high-performance intermetallic catalysts for practical applications.展开更多
The construction of heterojunctions in composite materials to optimize the electronic structures and active sites of energy materials is considered to be the promising strategy for the fabrication of high-performance ...The construction of heterojunctions in composite materials to optimize the electronic structures and active sites of energy materials is considered to be the promising strategy for the fabrication of high-performance electrochemical energy devices.In this paper,a one-step,easy processing and cost-effective technique for generating composite materials with heterojunctions was successfully developed.The composite containing Ni_(3)S_(4),NiS,and N-doped amorphous carbon(abbreviated as Ni_(3)S_(4)/NiS/NC)with multiple heterojunction nanosheets are synthesized via the space-confined effect of molten salt interface of recrystallized NaCl.Several lattice matching forms of Ni_(3)S_(4)with cubic structure and NiS with hexagonal structure are confirmed by the detailed characterization of heterogeneous interfaces.The C–S bonds are the key factor in realizing the chemical coupling between nickel sulfide and NC and constructing the stable heterojunction.Density functional theory calculations further revealed that the electronic interaction on the heterogeneous interface of Ni_(3)S_(4)/NiS can contribute to high electronic conductivity.The heterogeneous interfaces are identified to be the good electroactive region with excellent electrochemical performance.The synergistic effect of abundant active sites,the enhanced kinetic process and valid interface charge transfer channels of Ni_(3)S_(4)/NiS/NC multiple heterojunction can guarantee high reversible redox activity and high structural stability,resulting in both high specific capacitance and energy/power densities when it is used as the electrode for supercapacitors.This work offers a new avenue for the rational design of the heterojunction materials with improved electrochemical performance through space-confined effect of NaCl.展开更多
T4 polynucleotide kinase(T4 PNK) is a pivotal enzyme for DNA replication, recombination, and DNA damage repair. Herein, a robust single particle counting-based assay has been developed for the high-sensitive determina...T4 polynucleotide kinase(T4 PNK) is a pivotal enzyme for DNA replication, recombination, and DNA damage repair. Herein, a robust single particle counting-based assay has been developed for the high-sensitive determination of T4 PNK activity through only a simple one-step reaction. Taking benefit of the exceptional space-confined enzymatic property of T4 PNK towards DNA substrates on a single nanoparticle,the T4 PNK activity can be precisely determined by counting the fluorescence-positive nanoparticles in a digital manner with a total internal reflection fluorescent microscope(TIRFM). Due to the featured spatial-confined enzymatic property of T4 PNK and the single particle counting-based signal readout, T4PNK can be effectively differentiated from other interfering enzymes. This facile strategy has been also successfully applied to screen T4 PNK inhibitor and accurately determine T4 PNK activity in complex biological samples, paving a potential avenue for the digital analysis of biomarkers.展开更多
Atomically thin transition-metal dichalcogenide(TMDC) nanostructures are predicted to exhibit novel physical properties that make them attractive candidates for the fabrication of electronic and optoelectronic devices...Atomically thin transition-metal dichalcogenide(TMDC) nanostructures are predicted to exhibit novel physical properties that make them attractive candidates for the fabrication of electronic and optoelectronic devices. However, TMDCs tend to grow in the form of two-dimensional nanoplates(NPs) rather than one-dimensional nanoribbons(NRs) due to their native layered structure. Herein, we have developed a space-confined and substrate-directed chemical vapor deposition strategy for the controllable synthesis of WS2, WSe2, MoSe2, MoS2, WS2(1-x)Se2x NPs and NRs. TMDC NRs with lengths ranging from several micrometers to 100 μm have been obtained and the widths of TMDC NRs can be effectively tuned.Moreover, we found that TMDC NRs show different growth behaviors on van der Waals(vdW) and nonvd W substrates. The micro-nano structures, optical and electronic properties of synthesized TMDC NRs have been systematically investigated. This approach provides a general strategy for controllable synthesis of TMDC NRs, which makes these materials easily accessible as functional building blocks for novel optoelectronic devices.展开更多
As a lead-free perovskite,CsBi3I10 has attracted significant attention because of its high thermal tolerance and long electron diffusion length.Solution-processed high-performance CsBi3I10 perovskite devices,however,a...As a lead-free perovskite,CsBi3I10 has attracted significant attention because of its high thermal tolerance and long electron diffusion length.Solution-processed high-performance CsBi3I10 perovskite devices,however,are hindered by the formation of a two-dimensional structure,which results in an extremely high surface roughness and many pinholes.In this paper,we reported a space-confined growth(SCG)method using a single-layer polystyrene(PS)sphere template to obtain high-smoothness,high-crystallinity,and dense CsBi3I10 perovskite films.Compared with traditionally spin-coated CsBi3I10 photodetectors(PDs),the metal-semiconductor-metal PDs made by SCG showed a higher photocurrent,a lower dark current,and a bigger on/off ratio.In addition,the photocurrent of our unencapsulated CsBi3I10 perovskite PDs was not attenuated under long-time illumination.In addition,when the device was stored in air for 30 d,its performance also showed no degradation,demonstrating ultra-high stability.Furthermore,the synthesis was free of antisolvents,such as chlorobenzene and toluene,which is beneficial for the environmentally friendly assembly of the devices.Our strategy opens up a new way to prepare high-quality lead-free perovskite,which may be useful for applications in light-emitting diodes and solar cells.展开更多
The Fe single-atom catalyst(Fe-N-C)with Fe-N_(x) active sites is considered a promising alternative to Pt-based catalysts for oxygen reduction reaction(ORR).However,the exposure and utilization efficiency of the Fe-Nx...The Fe single-atom catalyst(Fe-N-C)with Fe-N_(x) active sites is considered a promising alternative to Pt-based catalysts for oxygen reduction reaction(ORR).However,the exposure and utilization efficiency of the Fe-Nx site in Fe-N-C lead to a certain competitive distance with Pt-based catalysts in the ORR process.Herein,a space-confinement strategy triggered by SiO_(2) templates to optimize the ORR triple-phase boundary of Fe-N-C,is reported.As expected,the optimized SiO_(2)(4)/Fe-N-C exhibits excellent ORR activity with a half-wave potential of 0.886 V in 0.1 M KOH.More importantly,the E_(1/2) loss of SiO_(2)(4)/Fe-N-C is merely 32 mV after 30,000 cycles.Density functional theory(DFT)calculations confirm SiO_(2)-induced carbon defects critically modulate electronic configurations of FeN_(4) centers,optimizing adsorption energetics of oxygen intermediates.Remarkably,when utilized as air cathodes for zinc-air batteries(ZABs),the device based on SiO_(2)(4)/Fe-N-C displays record-breaking power density(444.10 mW·cm^(-2))with superior long-term durability over 1013 h,outperforming most reported noble-metal-free electrocatalysts.This work provides a new route to optimize the triple-phase boundary of single-atom catalysts for energy storage applications.展开更多
As a distinct type of nanocapsules,hollow superstructures of inorganic nanoparticles have attracted increasing attention due to their controllable permeability,convenient functionalization,and efficient surface utiliz...As a distinct type of nanocapsules,hollow superstructures of inorganic nanoparticles have attracted increasing attention due to their controllable permeability,convenient functionalization,and efficient surface utilization.Conventionally,they are produced by assembling nanoparticles against expensive sacrificial templates.Herein,a general emulsion-based method is reported to assemble colloidal nanoparticles into submicron hollow superstructures,involving first co-assembly of colloidal nanoparticles with organic additives to form clusters,then overcoating the clusters with a polymer shell,and finally removing the organic additives and re-dispersing nanoparticles by exposing to a good solvent.The key to the success of this process is the re-assembly of nanoparticles against the polymer shells as driven by the capillary force during solvent evaporation,producing hollow superstructures.Such a space-confined assembly process can be well controlled by choice of solvents and their evaporation rates.This general technique provides an open and low-cost platform for creating hollow superstructures of various inorganic nanoparticles,offering many opportunities for exploring unique applications that can take advantage of the collective properties of the constituent nanoparticles and the permeable nanoshell structures.展开更多
基金financially supported by the National Natural Science Foundation of China(22379044,22472053)the Science and Technology Commission of Shanghai Municipality(23520710700)+6 种基金the Key Program of the National Natural Science Foundation of China(22239001)the Shanghai Pilot Program for Basic Research(22TQ1400100-5)the ShanghaiMunicipal Natural Science Foundation(25ZR1401081)the Fundamental Research Funds for the Central Universities(JKD01251505,JKVD1251041)the Postdoctoral Fellowship Program of CPSF(GZC20250071)the Shanghai Engineering Research Center of Hierarchical Nanomaterials(18DZ2252400)the Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism(Shanghai Municipal Education Commission)。
文摘The solution processibility of perovskites provides a costeffective and high-throughput route for fabricating state-of-the-art solar cells.However,the fast kinetics of precursor-to-perovskite transformation is susceptible to processing conditions,resulting in an uncontrollable variance in device performance.Here,we demonstrate a supramolecule confined approach to reproducibly fabricate perovskite films with an ultrasmooth,electronically homogeneous surface.The assembly of a calixarene capping layer on precursor surface can induce host-vip interactions with solvent molecules to tailor the desolvation kinetics,and initiate the perovskite crystallization from the sharp molecule-precursor interface.These combined effects significantly reduced the spatial variance and extended the processing window of perovskite films.As a result,the standard efficiency deviations of device-to-device and batch-to-batch devices were reduced from 0.64-0.26%to 0.67-0.23%,respectively.In addition,the perovskite films with ultrasmooth top surfaces exhibited photoluminescence quantum yield>10%and surface recombination velocities<100 cm s^(-1)for both interfaces that yielded p-i-n structured solar cells with power conversion efficiency over 25%.
基金financially supported by the National Key Research and Development Program(2018YFB1502503)the Sichuan Science and Technology Program(2020YJ0299)financial supports from the Australian Research Council under the future fellowship scheme(FT160100107)。
文摘Noble metal-based intermetallics are promising electrocatalysts for sustainable energy conversion and consumption processes.High-temperature pyrolysis(>500°C)methods are used to control their crystalline orderings,critical to their electrocatalytic activity and durability.However,the high temperature would cause severe aggregation,resulting in a low catalytic active surface area.Significant research efforts have been devoted to addressing this issue.This short review summarizes recent research progress on synthesizing noble metal-based intermetallic electrocatalysts by space-confined pyrolysis.We focus on three strategies:isolation in pores,coverture by shells,and immobilization by salts.The advantages and existing problems of different methods are highlighted.Last,important issues to be addressed in future research are also discussed.We hope that this article will stimulate future research to develop high-performance intermetallic catalysts for practical applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.U1804126,U21A2077 and U1804129)the Support Program of Science and Technology Innovation Leading Talent of Zhongyuan(Grant 204200510014)PhD program of Shanghai University and Program for Interdisciplinary Direction Team in Zhongyuan University of Technology.
文摘The construction of heterojunctions in composite materials to optimize the electronic structures and active sites of energy materials is considered to be the promising strategy for the fabrication of high-performance electrochemical energy devices.In this paper,a one-step,easy processing and cost-effective technique for generating composite materials with heterojunctions was successfully developed.The composite containing Ni_(3)S_(4),NiS,and N-doped amorphous carbon(abbreviated as Ni_(3)S_(4)/NiS/NC)with multiple heterojunction nanosheets are synthesized via the space-confined effect of molten salt interface of recrystallized NaCl.Several lattice matching forms of Ni_(3)S_(4)with cubic structure and NiS with hexagonal structure are confirmed by the detailed characterization of heterogeneous interfaces.The C–S bonds are the key factor in realizing the chemical coupling between nickel sulfide and NC and constructing the stable heterojunction.Density functional theory calculations further revealed that the electronic interaction on the heterogeneous interface of Ni_(3)S_(4)/NiS can contribute to high electronic conductivity.The heterogeneous interfaces are identified to be the good electroactive region with excellent electrochemical performance.The synergistic effect of abundant active sites,the enhanced kinetic process and valid interface charge transfer channels of Ni_(3)S_(4)/NiS/NC multiple heterojunction can guarantee high reversible redox activity and high structural stability,resulting in both high specific capacitance and energy/power densities when it is used as the electrode for supercapacitors.This work offers a new avenue for the rational design of the heterojunction materials with improved electrochemical performance through space-confined effect of NaCl.
基金supported by the National Natural Science Foundation of China (Nos. 22074088, 21622507, 21904083)the Program for Changjiang Scholars and Innovative Research Team in University (No. IRT_15R43)+1 种基金the Innovation Capability Support Program of Shaanxi (No. 2021TD-42)the Fundamental Research Funds for the Central Universities (Nos. GK202101001 and GK202201009)。
文摘T4 polynucleotide kinase(T4 PNK) is a pivotal enzyme for DNA replication, recombination, and DNA damage repair. Herein, a robust single particle counting-based assay has been developed for the high-sensitive determination of T4 PNK activity through only a simple one-step reaction. Taking benefit of the exceptional space-confined enzymatic property of T4 PNK towards DNA substrates on a single nanoparticle,the T4 PNK activity can be precisely determined by counting the fluorescence-positive nanoparticles in a digital manner with a total internal reflection fluorescent microscope(TIRFM). Due to the featured spatial-confined enzymatic property of T4 PNK and the single particle counting-based signal readout, T4PNK can be effectively differentiated from other interfering enzymes. This facile strategy has been also successfully applied to screen T4 PNK inhibitor and accurately determine T4 PNK activity in complex biological samples, paving a potential avenue for the digital analysis of biomarkers.
基金supported by the National Natural Science Foundation of China(11974301,11404274,11574395,11702236,61804050)the support from National Natural Science Foundation of China(21673054 and 11874130)+4 种基金the Science and Technology Project of Hunan Province(2019JJ30021,2018JJ3489)Grant from Education Commission of Hunan Province(18B084)Degree and Postgraduate Education Reform Project of Hunan Province(JG2018B045)the Program for Changjiang Scholars and Innovative Research Team in University(IRT13093)financial support from the research project of National University of Defense Technology(ZK18-03-38)。
文摘Atomically thin transition-metal dichalcogenide(TMDC) nanostructures are predicted to exhibit novel physical properties that make them attractive candidates for the fabrication of electronic and optoelectronic devices. However, TMDCs tend to grow in the form of two-dimensional nanoplates(NPs) rather than one-dimensional nanoribbons(NRs) due to their native layered structure. Herein, we have developed a space-confined and substrate-directed chemical vapor deposition strategy for the controllable synthesis of WS2, WSe2, MoSe2, MoS2, WS2(1-x)Se2x NPs and NRs. TMDC NRs with lengths ranging from several micrometers to 100 μm have been obtained and the widths of TMDC NRs can be effectively tuned.Moreover, we found that TMDC NRs show different growth behaviors on van der Waals(vdW) and nonvd W substrates. The micro-nano structures, optical and electronic properties of synthesized TMDC NRs have been systematically investigated. This approach provides a general strategy for controllable synthesis of TMDC NRs, which makes these materials easily accessible as functional building blocks for novel optoelectronic devices.
基金the National Natural Science Foundation of China(51972101 and 11874143)the Natural Science Foundation of Hubei Province(2019CFB508)Wuhan Yellow Crane Talent Program(2017-02)。
文摘As a lead-free perovskite,CsBi3I10 has attracted significant attention because of its high thermal tolerance and long electron diffusion length.Solution-processed high-performance CsBi3I10 perovskite devices,however,are hindered by the formation of a two-dimensional structure,which results in an extremely high surface roughness and many pinholes.In this paper,we reported a space-confined growth(SCG)method using a single-layer polystyrene(PS)sphere template to obtain high-smoothness,high-crystallinity,and dense CsBi3I10 perovskite films.Compared with traditionally spin-coated CsBi3I10 photodetectors(PDs),the metal-semiconductor-metal PDs made by SCG showed a higher photocurrent,a lower dark current,and a bigger on/off ratio.In addition,the photocurrent of our unencapsulated CsBi3I10 perovskite PDs was not attenuated under long-time illumination.In addition,when the device was stored in air for 30 d,its performance also showed no degradation,demonstrating ultra-high stability.Furthermore,the synthesis was free of antisolvents,such as chlorobenzene and toluene,which is beneficial for the environmentally friendly assembly of the devices.Our strategy opens up a new way to prepare high-quality lead-free perovskite,which may be useful for applications in light-emitting diodes and solar cells.
基金the National Key Research and Development Program of China(No.2022YFE0138900)the National Natural Science Foundation of China(No.21972017)+3 种基金the Shanghai Sailing Program(22YF1400700)the Chenguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission(22CGA37)the Fundamental Research Funds for the Central Universities and Graduate Student Innovation Fund of Donghua University(CUSF-DH-D-2024035)the Fundamental Research Funds for the Central Universities(2232022D-18).
文摘The Fe single-atom catalyst(Fe-N-C)with Fe-N_(x) active sites is considered a promising alternative to Pt-based catalysts for oxygen reduction reaction(ORR).However,the exposure and utilization efficiency of the Fe-Nx site in Fe-N-C lead to a certain competitive distance with Pt-based catalysts in the ORR process.Herein,a space-confinement strategy triggered by SiO_(2) templates to optimize the ORR triple-phase boundary of Fe-N-C,is reported.As expected,the optimized SiO_(2)(4)/Fe-N-C exhibits excellent ORR activity with a half-wave potential of 0.886 V in 0.1 M KOH.More importantly,the E_(1/2) loss of SiO_(2)(4)/Fe-N-C is merely 32 mV after 30,000 cycles.Density functional theory(DFT)calculations confirm SiO_(2)-induced carbon defects critically modulate electronic configurations of FeN_(4) centers,optimizing adsorption energetics of oxygen intermediates.Remarkably,when utilized as air cathodes for zinc-air batteries(ZABs),the device based on SiO_(2)(4)/Fe-N-C displays record-breaking power density(444.10 mW·cm^(-2))with superior long-term durability over 1013 h,outperforming most reported noble-metal-free electrocatalysts.This work provides a new route to optimize the triple-phase boundary of single-atom catalysts for energy storage applications.
文摘As a distinct type of nanocapsules,hollow superstructures of inorganic nanoparticles have attracted increasing attention due to their controllable permeability,convenient functionalization,and efficient surface utilization.Conventionally,they are produced by assembling nanoparticles against expensive sacrificial templates.Herein,a general emulsion-based method is reported to assemble colloidal nanoparticles into submicron hollow superstructures,involving first co-assembly of colloidal nanoparticles with organic additives to form clusters,then overcoating the clusters with a polymer shell,and finally removing the organic additives and re-dispersing nanoparticles by exposing to a good solvent.The key to the success of this process is the re-assembly of nanoparticles against the polymer shells as driven by the capillary force during solvent evaporation,producing hollow superstructures.Such a space-confined assembly process can be well controlled by choice of solvents and their evaporation rates.This general technique provides an open and low-cost platform for creating hollow superstructures of various inorganic nanoparticles,offering many opportunities for exploring unique applications that can take advantage of the collective properties of the constituent nanoparticles and the permeable nanoshell structures.
