This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped...This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped polybenzimidazole(PBI) membranes,including the use of carcinogenic monomers and complex synthesis procedures,this study aims to develop more cost-effective,readily synthesized,and high-performance alternatives.A series of superacid-catalyzed polyhydroxyalkylation reactions have been carefully designed between p-terphenyl and aldehydes bearing imidazole moieties,resulting in a new class of HT-PEMs.It is found that the chemical structure of aldehyde-substituted N-heterocycles significantly impacts the polymerization reaction.Specifically,the use of 1-methyl-2-imidazole-formaldehyde and 1 H-imidazole-4-formaldehyde monomers leads to the formation of high-viscosity,rigid,and ether-free polymers,denoted as PTIm-a and PTIm-b.Membranes fabricated from these polymers,due to their pendent imidazole groups,exhibit an exceptional capacity for PA absorption.Notably,PTIm-a,carrying methylimidazole moieties,demonstrates a superior chemical stability by maintaining morphology and structural stability during 350 h of Fenton testing.After being immersed in 75 wt% PA at 40℃,the PTIm-a membrane reaches a PA content of 152%,maintains a good tensile strength of 13.6 MPa,and exhibits a moderate conductivity of 50.2 mS cm^(-1) at 180℃.Under H_(2)/O_(2) operational conditions,a single cell based on the PTIm-a membrane attains a peak power density of 732 mW cm^(-2) at 180℃ without backpressure.Furthermore,the membrane demonstrates stable cycle stability over 173 h within 18 days at a current density of 200 mA cm^(-2),indicating its potential for practical application in HT-PEMFCs.This work highlights innovative strategies for the synthesis of advanced HT-PEMs,offering significant improvements in membrane properties and fuel cell performance,thus expanding the horizons of HT-PEMFC technology.展开更多
Ratiometric DNA biosensors,which utilize DNA as the recognition element and integrate dual signals from diverse sensing platforms including fluorescence,electrochemistry,and surface-enhanced Raman scattering(SERS),hav...Ratiometric DNA biosensors,which utilize DNA as the recognition element and integrate dual signals from diverse sensing platforms including fluorescence,electrochemistry,and surface-enhanced Raman scattering(SERS),have demonstrated remarkable proficiency in detecting a wide range of targets.In this review,we showcase the significant progress achieved by ratiometric biosensors.Firstly,ratiometric biosensors have made notable advancements in analyzing real samples.These include the analysis of pH values near cancer cells,quantification of miRNA in human cell lysates,detection of human telomerase RNA in cell extracts,and performing DNA logicgated in situ bioimaging on cell membranes.Secondly,excellent sensitivity has been attained through the utilization of effective amplification methods such as RCA,HCR,and CHA,among others.Thirdly,the construction of stable reference signals has resulted in significantly improved precision for ratiometric biosensors.This breakthrough has overcome matrix effects,enabling reliable detection in real samples with high selectivity.This review provides a comprehensive overview of recent advancements in strategies employed by ratiometric DNA biosensors.We present three types of biosensors based on distinct sensing platforms:fluorescent,electrochemical,and SERS biosensors.Additionally,we discuss future directions and primary challenges in the development of ratiometric DNA biosensors.展开更多
Construction of multi-channels of photo-carrier migration in photocatalysts is favor to boost conversion efficiency of solar energy by promoting the charge separation and transfer.Herein,a ternary ZnIn_(2)S_(4)/g-C_(3...Construction of multi-channels of photo-carrier migration in photocatalysts is favor to boost conversion efficiency of solar energy by promoting the charge separation and transfer.Herein,a ternary ZnIn_(2)S_(4)/g-C_(3)N_(4)/Ti_(3)C_(2) MXene hybrid composed of S-scheme junction integrated Schottky-junction was fabricated using a simple hydrothermal approach.All the components(g-C_(3)N_(4),ZnIn_(2)S_(4) and Ti_(3)C_(2) MXene)demonstrated two-dimensional(2D)nanosheets structure,leading to the formation of a 2D/2D/2D sandwich-like structure with intimate large interface for carrier migration.Furthermore,the photogenerated carriers on the g-C_(3)N_(4) possessed dual transfer channels,including one route in S-scheme transfer mode between the g-C_(3)N_(4) and ZnIn_(2)S_(4) and the other route in Schottky-junction between g-C_(3)N_(4) and Ti_(3)C_(2) MXene.Consequently,a highly efficient carrier separation and transport was realized in the ZnIn_(2)S_(4)/g-C_(3)N_(4)/Ti_(3)C_(2) MXene heterojunction.This ternary sample exhibited wide light response from 200 to 1400 nm and excellent photocatalytic H_(2) evolution of 2452.1μmol∙g^(–1)∙h^(–1),which was 200,3,1.5 and 1.6 times of g-C_(3)N_(4),ZnIn_(2)S_(4),ZnIn_(2)S_(4)/Ti_(3)C_(2) MXene and g-C_(3)N_(4)/ZnIn_(2)S_(4) binary composites.This work offers a paradigm for the rational construction of multi-electron pathways to regulate the charge separation and migration via the introduction of dual-junctions in catalytic system.展开更多
Durable and inexpensive graphitic carbon nitride(g-C_(3)N_(4))demonstrates great potential for achieving efficient photocatalytic hydrogen evolution reduction(HER).To further improve its activity,g-C_(3)N_(4)was subje...Durable and inexpensive graphitic carbon nitride(g-C_(3)N_(4))demonstrates great potential for achieving efficient photocatalytic hydrogen evolution reduction(HER).To further improve its activity,g-C_(3)N_(4)was subjected to atomic-level structural engineering by doping with transition metals(M=Fe,Co,or Ni),which simultaneously induced the formation of metal-N active sites in the g-C_(3)N_(4)framework and modulated the bandgap of g-C_(3)N_(4).Experiments and density functional theory calculations further verified that the as-formed metal-N bonds in M-doped g-C_(3)N_(4)acted as an"electron transfer bridge",where the migration of photo-generated electrons along the bridge enhanced the efficiency of separation of the photogenerated charges,and the optimized bandgap of g-C_(3)N_(4)afforded stronger reduction ability and wider light absorption.As a result,doping with either Fe,Co,or Ni had a positive effect on the HER activity,where Co-doped g-C_(3)N_(4)exhibited the highest performance.The findings illustrate that this atomic-level structural engineering could efficiently improve the HER activity and inspire the design of powerful photocatalysts.展开更多
An S-scheme heterojunction photocatalyst is capable of boosting photogenerated carrier separation and transfer,thus maintaining high photooxidation and photoredox ability.Herein,a 0D Ag_(3)PO_(4) nanoparticles(NPs)/1D...An S-scheme heterojunction photocatalyst is capable of boosting photogenerated carrier separation and transfer,thus maintaining high photooxidation and photoredox ability.Herein,a 0D Ag_(3)PO_(4) nanoparticles(NPs)/1D TiO_(2) nanofibers(NFs)S-scheme heterojunction with intimate interfacial contact was designed via the the hydro-thermal method.Benefiting from the abundant hydroxyl groups and size confinement effect of TiO_(2) NFs,the average diameter of the Ag_(3)PO_(4) nanoparticles decreased from 100 to 22 nm,which favored the construction of a 0D/1D geometry heterojunction.The multifunctional Ag_(3)PO_(4)/TiO_(2) sample exhibited excellent photocatalytic activity and stability in photocatalytic oxygen production(726μmol/g/h)and photocatalytic degradation of various organic contaminants such as rhodamine B(100%),phenol(60%)and tetracycline hydrochloride(100%).The significant improvements in the photocatalytic performance and stability can be attributed to the intimate interfacial contacts and rich active sites of 0D/1D geometry,fast charge carrier migration,and outstanding photoredox properties induced by the S-scheme charge-transfer route.This work offers a promising strategy for constructing 0D/1D S-scheme heterojunction photocatalysts for improved photocatalytic performance.展开更多
Photocatalytic water splitting is beneficial for the effective mitigation of global energy and environmental crises.Owing to multi-exciton generation,impressive light harvesting,and excellent photochemical properties,...Photocatalytic water splitting is beneficial for the effective mitigation of global energy and environmental crises.Owing to multi-exciton generation,impressive light harvesting,and excellent photochemical properties,the quantum dot(QD)-based catalysts reveal a considerable potential in photocatalytic hydrogen(H_(2))production compared with bulk competitors.In this review,we summarize the recent advances in QDs for photocatalytic H_(2) production by enumerating different synthetic and characterization strategies for QDs.Various QDs-based photocatalysts are introduced and summarized in categories,and the role of different QDs in varied systems,as well as the mechanism and key factors that enhance the photocatalytic H_(2) generation performance,is discussed.Finally,conclusions and future perspectives in the exploration of highly efficient QDs-based photocatalysts for innovative applications are highlighted.展开更多
Simultaneous generation of H_(2) fuel and value-added chemicals has attracted increasing attention since the photogenerated electrons and holes can be both employed to convert solar light into chemical energy.Herein,f...Simultaneous generation of H_(2) fuel and value-added chemicals has attracted increasing attention since the photogenerated electrons and holes can be both employed to convert solar light into chemical energy.Herein,for realizing UV-visible-NIR light driven dehydrogenation of benzyl alcohol(BA)into benzaldehydes(BAD)and H_(2),a novel localized surface plasmon resonance(LSPR)enhanced S-scheme heterojunction was designed by combining noble-metal-free plasmon MoO_(3-x) as oxidation semiconductor and Zn_(0.1)Cd_(0.9)S as reduction semiconductor.The photoredox system of Zn_(0.1)Cd_(0.9)S/MoO_(3-x) displayed an unconventional reaction model,in which the BA served as both electron donor and acceptor.The S-scheme charge transfer mechanism induced by the formed internal electric field enhanced the redox ability of charge carriers thermodynamically and boosted charge separation kinetically.Moreover,due to the LSPR effect of MoO_(3-x) nanosheets,Zn_(0.1)Cd_(0.9)S/MoO_(3-x) photocatalysts exhibited strong absorption in the region of full solar spectrum.Therefore,the Zn_(0.1)Cd_(0.9)S/MoO_(3-x) composite generated H_(2) and BAD simultaneously via selective oxidation of BA with high production(34.38 and 33.83 mmol×g^(–1) for H_(2) and BAD,respectively)upon full solar illumination.Even under NIR light irradiation,the H_(2) production rate could up to 94.5 mmol×g^(–1)×h^(–1).In addition,the Zn_(0.1)Cd_(0.9)S/MoO_(3-x) composite displayed effective photocatalytic H_(2) evolution rate up to 149.2 mmol×g^(–1)×h^(–1) from water,which was approximate 6 times that of pure Zn_(0.1)Cd_(0.9)S.This work provides a reference for rational design of plasmonic S-scheme heterojunction photocatalysts for coproduction of high-value chemicals and solar fuel production.展开更多
The mechanics-corrosion and strength-ductility tradeoffs of magnesium(Mg)alloys have limited their applications in fields such as orthopedic implants.Herein,a fine-grain structure consisting of weak anodic nano-lamell...The mechanics-corrosion and strength-ductility tradeoffs of magnesium(Mg)alloys have limited their applications in fields such as orthopedic implants.Herein,a fine-grain structure consisting of weak anodic nano-lamellar solute-enriched stacking faults(SESFs)with the average thickness of 8 nm and spacing of 16 nm is constructed in an as-extruded Mg96.9Y1.2Ho1.2Zn0.6Zr0.1(at.%)alloy,obtaining a high yield strength(YS)of 370 MPa,an excellent elongation(EL)of 17%,and a low corrosion rate of 0.30 mm y−1(close to that of high-pure Mg)in a uniform corrosion mode.Through scanning Kelvin probe force microscopy(SKPFM),one-dimensional nanostructured SESFs are identified as the weak anode(∼24 mV)for the first time.The excellent corrosion resistance is mainly related to the weak anodic nature of SESFs and their nano-lamellar structure,leading to the more uniform potential distribution to weaken galvanic corrosion and the release of abundant Y^(3+)/Ho^(3+)from SESFs to form a more protective film with an outer Ca_(10)(PO_(4))_(6)(OH)_(2)/Y_(2)O_(3)/Ho_(2)O_(3) layer(thickness percentage of this layer:72.45%).For comparison,the as-cast alloy containing block 18R long period stacking ordered(LPSO)phase and the heat-treated alloy with fine lamellar 18R-LPSO phase(thickness:80 nm,spacing:120 nm)are also studied,and the characteristics of SESFs and 18R-LPSO phase,such as the weak anode nature of the former and the cathode nature of the latter(37-90 mV),are distinguished under the same alloy composition.Ultimately,we put forward the idea of designing Mg alloys with high mechanical and anti-corrosion properties by constructing"homogeneous potential strengthening microstructure",such as the weak anode nano-lamellar SESFs structure.展开更多
Stapes fracture causes hearing loss and instability in the middle ear hearing system(MEHS). The material used in the stapes reconstruction restores stapes, but the effects of the nonlinear material parameters on the s...Stapes fracture causes hearing loss and instability in the middle ear hearing system(MEHS). The material used in the stapes reconstruction restores stapes, but the effects of the nonlinear material parameters on the stability of the MEHS are still unknown. To address this challenge, the nonlinear dynamic response and stability of the stapes reconstruction are investigated using a multi-degree-of-freedom mechanical model. The material parameters of the implant are tentatively determined by analyzing the natural frequencies of the undamped system. The dynamical properties of the MEHS are characterized under different external excitations. The approximate solution of the MEHS near the resonant frequency is derived through the multiple-time-scale method(MTSM). The results show that the nonlinear stiffness of the material has little influence on the MEHS in the healthy state, but it causes resonant phenomena between the ossicle and the implant in the pathological state.展开更多
A kind of dielectric barrier discharge（DBD） device composed of water electrodes with 3×3forms can produce large-area low-temperature plasmas at atmospheric pressure.To reflect the discharge characteristics of D...A kind of dielectric barrier discharge（DBD） device composed of water electrodes with 3×3forms can produce large-area low-temperature plasmas at atmospheric pressure.To reflect the discharge characteristics of DBD better,a dynamic simulation model,which is based on the voltage controlled current source（CCS）,is established,then the established model in Matlab/Simulink is used to simulate the DBD in air.The voltage-current waves and Lissajous at a voltage of 10 kV,11 kV and 12 kV peak value with a frequency of 15 kHz are studied.The change of the discharge power of DBD with a different amplitude and frequency of applied voltage is also analyzed.The result shows the voltage-current waves,Lissajous and discharge power of DBD under different conditions from the simulation agree well with those of the experiment.In addition,we propose a method to calculate the dielectric barrier capacitance Cd and the gap capacitance Cg,which is valid through analyzing the variation of capacitance at different voltage amplitudes.展开更多
Transferring high-quality exfoliated graphene flakes onto different substrates while keeping the graphene free of polymer residues is of great importance, but at the same time very challenging. Currently, the only fea...Transferring high-quality exfoliated graphene flakes onto different substrates while keeping the graphene free of polymer residues is of great importance, but at the same time very challenging. Currently, the only feasible way is the so-called all-dry "pick-and-lift" method, in which a hexagonal boron nitride(hBN) flake is employed to serve as a stamp to pick up graphene from one substrate and to lift it down onto another substrate. The transferred graphene samples, however,are always covered or encapsulated by hBN flakes, which leads to difficulties in further characterizations. Here, we report an improved "pick-and-lift" method, which allows ultra-clean graphene flakes to be transferred onto a variety of substrates without hBN coverage. Basically, by exploiting the superlubricity at the graphene/hBN stack interface, we are able to remove the top-layer hBN stamp by applying a tangential force and expose the underneath graphene.展开更多
Single-walled carbon nanotubes(SWCNTs),due to their outstanding electrical and optical properties,are expected to have extensive applications,such as in transparent conductive fims and ultra-small field-effect transis...Single-walled carbon nanotubes(SWCNTs),due to their outstanding electrical and optical properties,are expected to have extensive applications,such as in transparent conductive fims and ultra-small field-effect transistors(FETs).However,those applications can only be best realized with pure metallic or pure semiconducting SWCNTs.Hence,identifying and separating metallic from semiconducting SWCNTs in as-grown samples are crucial.In addition,knowledge of the type of an SWCNT is also important for further exploring its new properties in fundamental science.Here we report employing scanning near-field optical microscopy(SNOM)as a direct and simple method to identify metallic and semiconducting SWCNTs on SiO2/Si substrates.Metallic and semiconducting SWCNTs show distinct near-field optical responses because the metallic tubes support plasmons whereas the semiconducting tubes do not.The reliability of this method is verified using FET testing and Rayleigh scattering spectroscopy.Our result demonstrates that the SNOM technique provides a reliable,simple,noninvasive and in situ method to distinguish between metallic and semiconducting SWCNTs.展开更多
High temperature proton exchange membrane fuel cells(HT-PEMFCs)operating at elevated temperatures above 120℃ take advantage of feasible anode fuels and simplified water/heat management.A high temperature polymer elec...High temperature proton exchange membrane fuel cells(HT-PEMFCs)operating at elevated temperatures above 120℃ take advantage of feasible anode fuels and simplified water/heat management.A high temperature polymer electrolyte membrane(HT-PEM)is the core material for HT-PEMFCs.In this work,a series of phosphoric acid(PA)doped HT-PEMs based on poly(terphenyl piperidine)(PTP)tailored with alkyl groups are synthesized.Five different pendant alkyl groups(including methyl,propyl,pentyl,heptyl and decyl)are grafted onto the piperidine group through the Menshutkin reaction between PTP and alkyl halides.Compared with PTP and methyl grafted PTP(PTP-C1)membranes,the PTP-Cx membranes with long alkyl side chains exhibit improved PA doping contents and conductivities.The optimized pentylsubstituted PTP membrane(PTP-C5)possessed a reasonable PA doping content(202%after immersing in 85 wt%PA at 60℃),high proton conductivity(96 mS cm^(-1) at 180℃)and good tensile strength(4.6 MPa at room temperature).A H_(2)–air single cell equipped with PTP-C5/PA consequently achieved a high peak power density of 676 mW cm^(-2) at 210℃ without any humidification or backpressure.Thus,this work provides a simple method for preparing high-performance HT-PEMs.展开更多
Injectability empowers conductive hydrogels to transcend traditional limitations,unlocking a realm of possibilities for innovative medical,wearable,and therapeutic applications that can significantly enhance patient c...Injectability empowers conductive hydrogels to transcend traditional limitations,unlocking a realm of possibilities for innovative medical,wearable,and therapeutic applications that can significantly enhance patient care and quality of life.Here,we report an injectable,self-healable,and reusable hydrogel obtained by mixing the concentrated poly(3,4-ethylenedioxythiophene)doped with polystyrene sulfonate(PEDOT:PSS)suspension(~2 wt.%solid content),polyvinyl alcohol(PVA),and borax.Leveraging the presence of reversible borax/hydroxyl bonds and multiple hydrogen bonds,this PEDOT:PSS/PVA hydrogel exhibits notable shear-thinning behavior and self-healing capabilities,enabling it to be injected as a gel fiber from a syringe.As-prepared injectable hydrogel also demonstrates an ultra-low modulus(~2.5 MPa),reduced on-skin impedance(~45%of commercial electrodes),and high signal-to-noise ratio(SNR)(~15-22 dB)in recording of electrocardiography(ECG),electromyography(EMG),and electroencephalogram(EEG)signals.Furthermore,the injectable hydrogels can be remolded and reinjected as the reusable electrodes,maintaining nearly identical electrophysiological recording capabilities and brain-computer interface(BCI)performance compared to commercial wet electrodes.With their straightforward fabrication,excellent material properties and electronic performance,ease of cleaning,and remarkable reusability,our injectable PEDOT:PSS/PVA hydrogels hold promise for advancements in BCI based electronics and wearable bioelectronics.展开更多
In the green energy and carbon-neutral technology,electrochemical energy storage devices have received continuously increasing attention recently.However,due to the unavoidable volume expansion/shrinkage of key materi...In the green energy and carbon-neutral technology,electrochemical energy storage devices have received continuously increasing attention recently.However,due to the unavoidable volume expansion/shrinkage of key materials or irreversible mechanical damages during application,the stability of energy storage and delivery as well as the lifetime of these devices are severely shortened,leading to serious performance degradation or even safety issues.Therefore,the utilization of self-healable gels into electrochemical energy storage devices,such as electrodes,binders,and electrolytes,is proven as an effective method to realize long-term stable operation of these devices via the self-repairing of mechanical and electrochemical characteristics.Herein,this review first summarizes the feature and fabrication of different gels,paying special attention to hydrogels,organohydrogels,and ionogels.Then,basic concepts and figure of merit of self-healable gels are analyzed with a detailed discussion at the healing mechanisms,from reversible dynamic bonds to physical molecular diffusion,and to external healing trigger.Then we introduce all the important parts of electrochemical energy storage devices,which could be replaced by healable gels to enhance the durability,including electrodes,binders,and electrolytes.Finally,the critical challenges and future perspectives regarding the future development of healable gels based high-performance electrochemical energy storage devices or electronics are provided.展开更多
基金Natural Science Foundation of China (51603031)Liaoning Provincial Natural Science Foundation of China (2020-MS-087)China Scholarship Council(202306080157)。
文摘This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped polybenzimidazole(PBI) membranes,including the use of carcinogenic monomers and complex synthesis procedures,this study aims to develop more cost-effective,readily synthesized,and high-performance alternatives.A series of superacid-catalyzed polyhydroxyalkylation reactions have been carefully designed between p-terphenyl and aldehydes bearing imidazole moieties,resulting in a new class of HT-PEMs.It is found that the chemical structure of aldehyde-substituted N-heterocycles significantly impacts the polymerization reaction.Specifically,the use of 1-methyl-2-imidazole-formaldehyde and 1 H-imidazole-4-formaldehyde monomers leads to the formation of high-viscosity,rigid,and ether-free polymers,denoted as PTIm-a and PTIm-b.Membranes fabricated from these polymers,due to their pendent imidazole groups,exhibit an exceptional capacity for PA absorption.Notably,PTIm-a,carrying methylimidazole moieties,demonstrates a superior chemical stability by maintaining morphology and structural stability during 350 h of Fenton testing.After being immersed in 75 wt% PA at 40℃,the PTIm-a membrane reaches a PA content of 152%,maintains a good tensile strength of 13.6 MPa,and exhibits a moderate conductivity of 50.2 mS cm^(-1) at 180℃.Under H_(2)/O_(2) operational conditions,a single cell based on the PTIm-a membrane attains a peak power density of 732 mW cm^(-2) at 180℃ without backpressure.Furthermore,the membrane demonstrates stable cycle stability over 173 h within 18 days at a current density of 200 mA cm^(-2),indicating its potential for practical application in HT-PEMFCs.This work highlights innovative strategies for the synthesis of advanced HT-PEMs,offering significant improvements in membrane properties and fuel cell performance,thus expanding the horizons of HT-PEMFC technology.
基金financially supported by:The National Quality Infrastructure Program of China(2021YFF0600705 NQI)the Natural Science Foundation of China(No.22074093).
文摘Ratiometric DNA biosensors,which utilize DNA as the recognition element and integrate dual signals from diverse sensing platforms including fluorescence,electrochemistry,and surface-enhanced Raman scattering(SERS),have demonstrated remarkable proficiency in detecting a wide range of targets.In this review,we showcase the significant progress achieved by ratiometric biosensors.Firstly,ratiometric biosensors have made notable advancements in analyzing real samples.These include the analysis of pH values near cancer cells,quantification of miRNA in human cell lysates,detection of human telomerase RNA in cell extracts,and performing DNA logicgated in situ bioimaging on cell membranes.Secondly,excellent sensitivity has been attained through the utilization of effective amplification methods such as RCA,HCR,and CHA,among others.Thirdly,the construction of stable reference signals has resulted in significantly improved precision for ratiometric biosensors.This breakthrough has overcome matrix effects,enabling reliable detection in real samples with high selectivity.This review provides a comprehensive overview of recent advancements in strategies employed by ratiometric DNA biosensors.We present three types of biosensors based on distinct sensing platforms:fluorescent,electrochemical,and SERS biosensors.Additionally,we discuss future directions and primary challenges in the development of ratiometric DNA biosensors.
文摘Construction of multi-channels of photo-carrier migration in photocatalysts is favor to boost conversion efficiency of solar energy by promoting the charge separation and transfer.Herein,a ternary ZnIn_(2)S_(4)/g-C_(3)N_(4)/Ti_(3)C_(2) MXene hybrid composed of S-scheme junction integrated Schottky-junction was fabricated using a simple hydrothermal approach.All the components(g-C_(3)N_(4),ZnIn_(2)S_(4) and Ti_(3)C_(2) MXene)demonstrated two-dimensional(2D)nanosheets structure,leading to the formation of a 2D/2D/2D sandwich-like structure with intimate large interface for carrier migration.Furthermore,the photogenerated carriers on the g-C_(3)N_(4) possessed dual transfer channels,including one route in S-scheme transfer mode between the g-C_(3)N_(4) and ZnIn_(2)S_(4) and the other route in Schottky-junction between g-C_(3)N_(4) and Ti_(3)C_(2) MXene.Consequently,a highly efficient carrier separation and transport was realized in the ZnIn_(2)S_(4)/g-C_(3)N_(4)/Ti_(3)C_(2) MXene heterojunction.This ternary sample exhibited wide light response from 200 to 1400 nm and excellent photocatalytic H_(2) evolution of 2452.1μmol∙g^(–1)∙h^(–1),which was 200,3,1.5 and 1.6 times of g-C_(3)N_(4),ZnIn_(2)S_(4),ZnIn_(2)S_(4)/Ti_(3)C_(2) MXene and g-C_(3)N_(4)/ZnIn_(2)S_(4) binary composites.This work offers a paradigm for the rational construction of multi-electron pathways to regulate the charge separation and migration via the introduction of dual-junctions in catalytic system.
文摘Durable and inexpensive graphitic carbon nitride(g-C_(3)N_(4))demonstrates great potential for achieving efficient photocatalytic hydrogen evolution reduction(HER).To further improve its activity,g-C_(3)N_(4)was subjected to atomic-level structural engineering by doping with transition metals(M=Fe,Co,or Ni),which simultaneously induced the formation of metal-N active sites in the g-C_(3)N_(4)framework and modulated the bandgap of g-C_(3)N_(4).Experiments and density functional theory calculations further verified that the as-formed metal-N bonds in M-doped g-C_(3)N_(4)acted as an"electron transfer bridge",where the migration of photo-generated electrons along the bridge enhanced the efficiency of separation of the photogenerated charges,and the optimized bandgap of g-C_(3)N_(4)afforded stronger reduction ability and wider light absorption.As a result,doping with either Fe,Co,or Ni had a positive effect on the HER activity,where Co-doped g-C_(3)N_(4)exhibited the highest performance.The findings illustrate that this atomic-level structural engineering could efficiently improve the HER activity and inspire the design of powerful photocatalysts.
文摘An S-scheme heterojunction photocatalyst is capable of boosting photogenerated carrier separation and transfer,thus maintaining high photooxidation and photoredox ability.Herein,a 0D Ag_(3)PO_(4) nanoparticles(NPs)/1D TiO_(2) nanofibers(NFs)S-scheme heterojunction with intimate interfacial contact was designed via the the hydro-thermal method.Benefiting from the abundant hydroxyl groups and size confinement effect of TiO_(2) NFs,the average diameter of the Ag_(3)PO_(4) nanoparticles decreased from 100 to 22 nm,which favored the construction of a 0D/1D geometry heterojunction.The multifunctional Ag_(3)PO_(4)/TiO_(2) sample exhibited excellent photocatalytic activity and stability in photocatalytic oxygen production(726μmol/g/h)and photocatalytic degradation of various organic contaminants such as rhodamine B(100%),phenol(60%)and tetracycline hydrochloride(100%).The significant improvements in the photocatalytic performance and stability can be attributed to the intimate interfacial contacts and rich active sites of 0D/1D geometry,fast charge carrier migration,and outstanding photoredox properties induced by the S-scheme charge-transfer route.This work offers a promising strategy for constructing 0D/1D S-scheme heterojunction photocatalysts for improved photocatalytic performance.
基金Taishan Youth Scholar Program of Shandong ProvinceNational Natural Science Foundation of China,Grant/Award Numbers:21972058,21975110,22088102,51825205+3 种基金Postgraduate Practice Research Innovation Program of Jiangsu Province,Grant/Award Number:SJCX21_1707CAS Project for Young Scientists in Basic Research,Grant/Award Number:YSBR‐004DNL Cooperation Fund,CAS,Grant/Award Number:DNL202016National Key Projects for Fundamental Research and Development of China,Grant/Award Number:2018YFB1502002。
文摘Photocatalytic water splitting is beneficial for the effective mitigation of global energy and environmental crises.Owing to multi-exciton generation,impressive light harvesting,and excellent photochemical properties,the quantum dot(QD)-based catalysts reveal a considerable potential in photocatalytic hydrogen(H_(2))production compared with bulk competitors.In this review,we summarize the recent advances in QDs for photocatalytic H_(2) production by enumerating different synthetic and characterization strategies for QDs.Various QDs-based photocatalysts are introduced and summarized in categories,and the role of different QDs in varied systems,as well as the mechanism and key factors that enhance the photocatalytic H_(2) generation performance,is discussed.Finally,conclusions and future perspectives in the exploration of highly efficient QDs-based photocatalysts for innovative applications are highlighted.
文摘Simultaneous generation of H_(2) fuel and value-added chemicals has attracted increasing attention since the photogenerated electrons and holes can be both employed to convert solar light into chemical energy.Herein,for realizing UV-visible-NIR light driven dehydrogenation of benzyl alcohol(BA)into benzaldehydes(BAD)and H_(2),a novel localized surface plasmon resonance(LSPR)enhanced S-scheme heterojunction was designed by combining noble-metal-free plasmon MoO_(3-x) as oxidation semiconductor and Zn_(0.1)Cd_(0.9)S as reduction semiconductor.The photoredox system of Zn_(0.1)Cd_(0.9)S/MoO_(3-x) displayed an unconventional reaction model,in which the BA served as both electron donor and acceptor.The S-scheme charge transfer mechanism induced by the formed internal electric field enhanced the redox ability of charge carriers thermodynamically and boosted charge separation kinetically.Moreover,due to the LSPR effect of MoO_(3-x) nanosheets,Zn_(0.1)Cd_(0.9)S/MoO_(3-x) photocatalysts exhibited strong absorption in the region of full solar spectrum.Therefore,the Zn_(0.1)Cd_(0.9)S/MoO_(3-x) composite generated H_(2) and BAD simultaneously via selective oxidation of BA with high production(34.38 and 33.83 mmol×g^(–1) for H_(2) and BAD,respectively)upon full solar illumination.Even under NIR light irradiation,the H_(2) production rate could up to 94.5 mmol×g^(–1)×h^(–1).In addition,the Zn_(0.1)Cd_(0.9)S/MoO_(3-x) composite displayed effective photocatalytic H_(2) evolution rate up to 149.2 mmol×g^(–1)×h^(–1) from water,which was approximate 6 times that of pure Zn_(0.1)Cd_(0.9)S.This work provides a reference for rational design of plasmonic S-scheme heterojunction photocatalysts for coproduction of high-value chemicals and solar fuel production.
基金the support of the National Natural Science Foundation of China(51871069,52071093)the Zhejiang Province Key Research and Development Plan,China(2021C01086)Student Research and Innovation Fund of the Fundamental Research Funds for the Central Universities(3072022GIP1004)。
文摘The mechanics-corrosion and strength-ductility tradeoffs of magnesium(Mg)alloys have limited their applications in fields such as orthopedic implants.Herein,a fine-grain structure consisting of weak anodic nano-lamellar solute-enriched stacking faults(SESFs)with the average thickness of 8 nm and spacing of 16 nm is constructed in an as-extruded Mg96.9Y1.2Ho1.2Zn0.6Zr0.1(at.%)alloy,obtaining a high yield strength(YS)of 370 MPa,an excellent elongation(EL)of 17%,and a low corrosion rate of 0.30 mm y−1(close to that of high-pure Mg)in a uniform corrosion mode.Through scanning Kelvin probe force microscopy(SKPFM),one-dimensional nanostructured SESFs are identified as the weak anode(∼24 mV)for the first time.The excellent corrosion resistance is mainly related to the weak anodic nature of SESFs and their nano-lamellar structure,leading to the more uniform potential distribution to weaken galvanic corrosion and the release of abundant Y^(3+)/Ho^(3+)from SESFs to form a more protective film with an outer Ca_(10)(PO_(4))_(6)(OH)_(2)/Y_(2)O_(3)/Ho_(2)O_(3) layer(thickness percentage of this layer:72.45%).For comparison,the as-cast alloy containing block 18R long period stacking ordered(LPSO)phase and the heat-treated alloy with fine lamellar 18R-LPSO phase(thickness:80 nm,spacing:120 nm)are also studied,and the characteristics of SESFs and 18R-LPSO phase,such as the weak anode nature of the former and the cathode nature of the latter(37-90 mV),are distinguished under the same alloy composition.Ultimately,we put forward the idea of designing Mg alloys with high mechanical and anti-corrosion properties by constructing"homogeneous potential strengthening microstructure",such as the weak anode nano-lamellar SESFs structure.
基金Project supported by the National Natural Science Foundation of China (Nos. 12072222, 12132010,12021002, 11991032, and 12372019)the State Key Laboratory of Mechanical Behavior and System Safety of Traffic Engineering Structures of China (No. SKLTESKF1901)the Aeronautical Science Foundation of China (No. ASFC-201915048001)。
文摘Stapes fracture causes hearing loss and instability in the middle ear hearing system(MEHS). The material used in the stapes reconstruction restores stapes, but the effects of the nonlinear material parameters on the stability of the MEHS are still unknown. To address this challenge, the nonlinear dynamic response and stability of the stapes reconstruction are investigated using a multi-degree-of-freedom mechanical model. The material parameters of the implant are tentatively determined by analyzing the natural frequencies of the undamped system. The dynamical properties of the MEHS are characterized under different external excitations. The approximate solution of the MEHS near the resonant frequency is derived through the multiple-time-scale method(MTSM). The results show that the nonlinear stiffness of the material has little influence on the MEHS in the healthy state, but it causes resonant phenomena between the ossicle and the implant in the pathological state.
基金supported by the National Natural Science Foundation of China(NSFC) under Contract No.10775055the special funds of State Key Laboratory of Advanced Elcctromag-netic Engineering and Technology,Huazhong University of Science and Technology(Grant No. 2014ZZ001)
文摘A kind of dielectric barrier discharge（DBD） device composed of water electrodes with 3×3forms can produce large-area low-temperature plasmas at atmospheric pressure.To reflect the discharge characteristics of DBD better,a dynamic simulation model,which is based on the voltage controlled current source（CCS）,is established,then the established model in Matlab/Simulink is used to simulate the DBD in air.The voltage-current waves and Lissajous at a voltage of 10 kV,11 kV and 12 kV peak value with a frequency of 15 kHz are studied.The change of the discharge power of DBD with a different amplitude and frequency of applied voltage is also analyzed.The result shows the voltage-current waves,Lissajous and discharge power of DBD under different conditions from the simulation agree well with those of the experiment.In addition,we propose a method to calculate the dielectric barrier capacitance Cd and the gap capacitance Cg,which is valid through analyzing the variation of capacitance at different voltage amplitudes.
基金Project supported by the National Key Research and Development Program of China(Grant No.2016YFA0302001)the National Natural Science Foundation of China(Grant Nos.11574204 and 11774224)
文摘Transferring high-quality exfoliated graphene flakes onto different substrates while keeping the graphene free of polymer residues is of great importance, but at the same time very challenging. Currently, the only feasible way is the so-called all-dry "pick-and-lift" method, in which a hexagonal boron nitride(hBN) flake is employed to serve as a stamp to pick up graphene from one substrate and to lift it down onto another substrate. The transferred graphene samples, however,are always covered or encapsulated by hBN flakes, which leads to difficulties in further characterizations. Here, we report an improved "pick-and-lift" method, which allows ultra-clean graphene flakes to be transferred onto a variety of substrates without hBN coverage. Basically, by exploiting the superlubricity at the graphene/hBN stack interface, we are able to remove the top-layer hBN stamp by applying a tangential force and expose the underneath graphene.
基金the National Natural Science Foundation of China under Grant Nos.11574204 and 11774224the National Key Research and Development Program of China(2016YFA0302001)+1 种基金Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learningadditional support from a Shanghai talent program。
文摘Single-walled carbon nanotubes(SWCNTs),due to their outstanding electrical and optical properties,are expected to have extensive applications,such as in transparent conductive fims and ultra-small field-effect transistors(FETs).However,those applications can only be best realized with pure metallic or pure semiconducting SWCNTs.Hence,identifying and separating metallic from semiconducting SWCNTs in as-grown samples are crucial.In addition,knowledge of the type of an SWCNT is also important for further exploring its new properties in fundamental science.Here we report employing scanning near-field optical microscopy(SNOM)as a direct and simple method to identify metallic and semiconducting SWCNTs on SiO2/Si substrates.Metallic and semiconducting SWCNTs show distinct near-field optical responses because the metallic tubes support plasmons whereas the semiconducting tubes do not.The reliability of this method is verified using FET testing and Rayleigh scattering spectroscopy.Our result demonstrates that the SNOM technique provides a reliable,simple,noninvasive and in situ method to distinguish between metallic and semiconducting SWCNTs.
基金We gratefully acknowledge the Natural Science Foundation of China(51603031)the Fundamental Research Funds for the Central Universities of China(N2005026).
文摘High temperature proton exchange membrane fuel cells(HT-PEMFCs)operating at elevated temperatures above 120℃ take advantage of feasible anode fuels and simplified water/heat management.A high temperature polymer electrolyte membrane(HT-PEM)is the core material for HT-PEMFCs.In this work,a series of phosphoric acid(PA)doped HT-PEMs based on poly(terphenyl piperidine)(PTP)tailored with alkyl groups are synthesized.Five different pendant alkyl groups(including methyl,propyl,pentyl,heptyl and decyl)are grafted onto the piperidine group through the Menshutkin reaction between PTP and alkyl halides.Compared with PTP and methyl grafted PTP(PTP-C1)membranes,the PTP-Cx membranes with long alkyl side chains exhibit improved PA doping contents and conductivities.The optimized pentylsubstituted PTP membrane(PTP-C5)possessed a reasonable PA doping content(202%after immersing in 85 wt%PA at 60℃),high proton conductivity(96 mS cm^(-1) at 180℃)and good tensile strength(4.6 MPa at room temperature).A H_(2)–air single cell equipped with PTP-C5/PA consequently achieved a high peak power density of 676 mW cm^(-2) at 210℃ without any humidification or backpressure.Thus,this work provides a simple method for preparing high-performance HT-PEMs.
基金This work was supported by the National Natural Science Foundation of China （Grant Nos. 41172110 and 61107090） and Shandong Provincial Natural Science Foundation （Grant No. ZR2011BZ007）.
基金the National Natural Science Foundation of China(Nos.62304112 and 62288102)Natural Science Foundation of Jiangsu Province of China(No.BK20230359)+1 种基金Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.22KJB430038)Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications(No.NY221111).
文摘Injectability empowers conductive hydrogels to transcend traditional limitations,unlocking a realm of possibilities for innovative medical,wearable,and therapeutic applications that can significantly enhance patient care and quality of life.Here,we report an injectable,self-healable,and reusable hydrogel obtained by mixing the concentrated poly(3,4-ethylenedioxythiophene)doped with polystyrene sulfonate(PEDOT:PSS)suspension(~2 wt.%solid content),polyvinyl alcohol(PVA),and borax.Leveraging the presence of reversible borax/hydroxyl bonds and multiple hydrogen bonds,this PEDOT:PSS/PVA hydrogel exhibits notable shear-thinning behavior and self-healing capabilities,enabling it to be injected as a gel fiber from a syringe.As-prepared injectable hydrogel also demonstrates an ultra-low modulus(~2.5 MPa),reduced on-skin impedance(~45%of commercial electrodes),and high signal-to-noise ratio(SNR)(~15-22 dB)in recording of electrocardiography(ECG),electromyography(EMG),and electroencephalogram(EEG)signals.Furthermore,the injectable hydrogels can be remolded and reinjected as the reusable electrodes,maintaining nearly identical electrophysiological recording capabilities and brain-computer interface(BCI)performance compared to commercial wet electrodes.With their straightforward fabrication,excellent material properties and electronic performance,ease of cleaning,and remarkable reusability,our injectable PEDOT:PSS/PVA hydrogels hold promise for advancements in BCI based electronics and wearable bioelectronics.
基金supported by the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications(No.NY221111)Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(No.22KJB430038)awarded to Y.L.Z.W.L.+1 种基金thanks the support from the National Natural Science Foundation Program of China(No.52204370)Open project of Hebei Key Laboratory of Hazardous Chemicals Safety and Control Technology(No.20211204-7).
文摘In the green energy and carbon-neutral technology,electrochemical energy storage devices have received continuously increasing attention recently.However,due to the unavoidable volume expansion/shrinkage of key materials or irreversible mechanical damages during application,the stability of energy storage and delivery as well as the lifetime of these devices are severely shortened,leading to serious performance degradation or even safety issues.Therefore,the utilization of self-healable gels into electrochemical energy storage devices,such as electrodes,binders,and electrolytes,is proven as an effective method to realize long-term stable operation of these devices via the self-repairing of mechanical and electrochemical characteristics.Herein,this review first summarizes the feature and fabrication of different gels,paying special attention to hydrogels,organohydrogels,and ionogels.Then,basic concepts and figure of merit of self-healable gels are analyzed with a detailed discussion at the healing mechanisms,from reversible dynamic bonds to physical molecular diffusion,and to external healing trigger.Then we introduce all the important parts of electrochemical energy storage devices,which could be replaced by healable gels to enhance the durability,including electrodes,binders,and electrolytes.Finally,the critical challenges and future perspectives regarding the future development of healable gels based high-performance electrochemical energy storage devices or electronics are provided.
