As a catalyst of the air cathode in zinc-air batteries,tungstic acid ferrous(FeWO_(4)),a nanoscale transition metal tungstate,shows a broad application prospect in the oxygen reduction reaction(ORR).While FeWO_(4)poss...As a catalyst of the air cathode in zinc-air batteries,tungstic acid ferrous(FeWO_(4)),a nanoscale transition metal tungstate,shows a broad application prospect in the oxygen reduction reaction(ORR).While FeWO_(4)possesses favorable electrochemical properties and thermodynamic stability,its intrinsic semiconductor characteristics result in a relatively slow electron transfer rate,limiting the ORR catalytic activity.In this work,the electronic structure of FeWO_(4)is significantly modulated by introducing phosphorus(P)atoms with abundant valence electrons.The P doping can adjust the electronic structure of FeWO_(4)and then optimize oxygen-containing intermediates'absorption/desorption efficiency to achieve improved ORR activity.Furthermore,the sodium chloride template is utilized to construct a porous carbon framework for anchoring phosphorus-doped iron tungstate(P-FeWO_(4)/PNC).The porous carbon skeleton provides numerous active sites for the absorption/desorption and redox reactions on the P-FeWO_(4)/PNC surface and serves as mass transport channels for reactants and intermediates.The P-FeWO_(4)/PNC demonstrates ORR performance(E1/2=0.86 V vs.RHE).Furthermore,the zinc-air batteries incorporating the P-FeWO_(4)/PNC composite demonstrate an increased peak power density(172.2 mW·cm^(-2)),high specific capacity(810.1 mAh·g^(-1)),and sustained long-term cycling stability lasting up to 240 h.This research not only contributes to the advancement of cost-effective tungsten-based non-precious metallic ORR catalysts,but also guides their utilization in zinc-air batteries.展开更多
Silica aerogel has broad applications in the field of high-temperature thermal insulation due to its low density,low thermal conductivity and high stability.However,its thermal insulation performance deteriorates sign...Silica aerogel has broad applications in the field of high-temperature thermal insulation due to its low density,low thermal conductivity and high stability.However,its thermal insulation performance deteriorates significantly at elevated temperatures exceeding 600℃,primarily due to the collapse of pore structure.Meanwhile,the shielding capacity of SiO_(2) aerogel to the infrared radiation at high temperature is rather low due to the intrinsic properties of SiO_(2).Herein,a strategy for improving the high-temperature stability and infrared shielding properties of SiO_(2) aerogel via Ca doping was explored.Calcium-doped silica aerogel(CSA)powders were prepared by Sol-Gel,hydrothermal,and ambient pressure drying(APD)techniques using water glass and anhydrous calcium chloride as precursors and trimethylchlorosilane as a hydrophobic modifier.The effects of Ca/Si molar ratio in the precursor and hydrothermal conditions(temperature and pH)on the crystalline properties,microscopic morphology and pore structure of CSAs were investigated.The results show that the Ca/Si molar ratio and hydrothermal treatment have significant effects on the microstructure and heat resistance of CSAs in the temperature range of 400-1000℃.The samples sintered at 1000℃have a high specific surface area of 100.1 m^(2)/g and a pore volume of 0.8705 cm^(3)/g,indicating that the CSA has good heat resistance.One-side insulation tests at temperatures up to 600℃show that the sample with a Ca/Si molar ratio of 1.0 has the best insulation performance,with a cold surface temperature of 450℃,which is 27℃lower than that of the pure silica aerogel.展开更多
Mn^(2+)-doped CsPbCl_(3)(Mn^(2+):CsPbCl_(3)) nanocrystals(NCs) have attracted considerable attention due to their unique strong and broad orange-red emission band,presenting promising applications in the field of phot...Mn^(2+)-doped CsPbCl_(3)(Mn^(2+):CsPbCl_(3)) nanocrystals(NCs) have attracted considerable attention due to their unique strong and broad orange-red emission band,presenting promising applications in the field of photoelectric devices.However,pristine Mn^(2+):CsPbCl_(3)NCs commonly suffer from low photoluminescence quantum yield(PL QY) and stability issues.Herein,we introduced europium ions(Eu^(3+))into Mn^(2+):CsPbCl_(3)NCs via the thermal injection synthesis method to obtain high performance Eu^(3+)and Mn^(2+)codoped CsPbCl_(3)(Eu^(3+)/Mn^(2+):CsPbCl_(3)) NCs.The maximum PL QY of the resulting Eu^(3+)/Mn^(2+):CsPbCl_(3)NCs reaches up to 90.92%.It is found that the doping of Eu^(3+)ions significantly reduces the non-radiative recombination caused by high defect states,and improves the energy transfer efficiency from exciton to Mn^(2+),thereby boosting the PL performance.Moreover,doping Eu^(3+)ions notably improves the UV-light and water stability of Mn^(2+):CsPbCl_(3)NCs.We further demonstrate the application versatility of Eu^(3+)/Mn^(2+):CsPbCl_(3)NCs in white light emitting diodes(WLEDs) and optical anticounterfeiting applications.This work provides a valuable perspective for the attainment of high performance Mn^(2+):CsPbCl_(3)NCs and lays a foundation for the codoping of other lanthanide ions to adjust the luminescence properties of Mn^(2+):CsPbCl_(3)NCs.展开更多
Herein,antibacterial silver‑doped fluorescent carbon dots(Ag‑CDs)were synthesized through a stepwise hydrothermal method,with polyethyleneimine(PEI),citric acid(CA),and silver nitrate(AgNO3)serving as precursors.The a...Herein,antibacterial silver‑doped fluorescent carbon dots(Ag‑CDs)were synthesized through a stepwise hydrothermal method,with polyethyleneimine(PEI),citric acid(CA),and silver nitrate(AgNO3)serving as precursors.The applicability and antimicrobial efficacy of these nanomaterials were systematically investigated for metal ion sensing.Experimental evidence demonstrated that the Ag‑CDs exhibited a pronounced fluorescence quenching response toward ferric ions(Fe^(3+)),enabling their quantitative determination via a linear concentration‑dependent relationship.These Ag‑CDs exhibited significant inhibitory effects on biofilm growth and disruption for both Escherichia coli and Staphylococcus aureus.Mechanism investigations indicate that Ag‑CDs induced the death of Escherichia coli and Pseudomonas aeruginosa by disrupting their bacterial morphology and structure,triggering the generation of intracellular reactive oxygen species(ROS),and impairing their antioxidant defense system.展开更多
Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon di...Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.展开更多
Synthetic dyes,particularly azo dyes,pose significant environmental and health risks due to their persistence,toxicity,and potential carcinogenicity.Zinc oxide(ZnO)is a promising photocatalyst for wastewater remediati...Synthetic dyes,particularly azo dyes,pose significant environmental and health risks due to their persistence,toxicity,and potential carcinogenicity.Zinc oxide(ZnO)is a promising photocatalyst for wastewater remediation,but its wide bandgap and rapid charge recombination limit its practical efficacy.Furthermore,conventional doping methods often rely on hazardous chemical precursors,undermining the sustainability of the overall approach.This review introduces a novel and sustainable paradigm:the utilization of biomass-derived precursors as green reagents for the in-situ synthesis and simultaneous phosphorus-nitrogen(P-N)co-doping of ZnO nanoparticles.We critically analyze how the intrinsic biochemical composition of biomass,rich in P,N,and other heteroatoms,facilitates this one-pot,eco-friendly functionalization.This integrated strategy merges the performance enhancement offered by advanced co-doping,such as extended visible-light absorption and suppressed charge recombination,with the core principles of green chemistry and circular economy.It offers a dual benefit:creating highly effective photocatalysts for the degradation of persistent pollutants and valorizing abundant agricultural or biological waste streams.Our comprehensive evaluation goes beyond description to critically assess the underlying mechanisms,comparative efficacy,scalability challenges,and future research directions of this emerging field.This review underscores the unique contribution of biomass-mediated synthesis to advancing sustainable nanotechnology for environmental applications.展开更多
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthes...Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthesized the electrode material Ce-NiCo-LDHs@SnO_(2)/NF through a two-step hydrothermal reaction,where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO_(2) layer.Ce doping adjusts the internal electronic distribution of Ni Co-LDHs,while the introduction of the SnO_(2) layer enhances electron transfer capability.Together,these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism(LOM).Consequently,Ce-NiCo-LDHs@SnO_(2)/NF exhibits high level electrochemical performance in OER,requiring only 234 m V overpotential to achieve a current density of 10 m A/cm^(2),with a Tafel slope of just 27.39 m V/dec.When paired with Pt/C/NF,an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 m A/cm^(2).Furthermore,the catalyst demonstrates stability for 100 h during the OWS stability test.This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO_(2) layer.展开更多
Hard carbon(HC)in sodium-ion batteries is searched by numerous investigations,which can offer the excellent performance of reversible Na^(+)insertion and extraction.The covalent heteroatom doping in HC is recently wor...Hard carbon(HC)in sodium-ion batteries is searched by numerous investigations,which can offer the excellent performance of reversible Na^(+)insertion and extraction.The covalent heteroatom doping in HC is recently worth concentrating,which can dilate the interlayer spacing of graphite to adjust the electrochemical storage performance in carbon anodes.However,the reported doping strategies of the modified HC have only resulted in limited improvement,especially unobvious effects on tuning porous structure.In this study,tannin extract and K_(2)SO_(4) are respectively utilized as carbon source and sulfur source for the fabrication of HC,in which K_(2)SO_(4) can contribute to the heteroatom doping,and the pore forming as well.The tannin-derived sulfur-doped carbon anode shows the excellent cycle stability,achieving a high reversible capacity of 520.5 mAh/g at a current density of 100 mA/g.Even after 500 cycles at a current density of 3 A/g,a high specific capacity of 236.7 mAh/g and a capacity retention rate of 92.6%can be reserved.Compared with the initial carbon,the adsorption energy of Na^(+)is multifold times higher,whereas Na^(+)diffusion energy barriers manyfold decrease.Moreover,the full battery assembled with Na_(3)V_(2)(PO_(4))_(3)/tannin-based HC demonstrates a stable cycling performance.This work can manifest the potentiality of the tannin-based electrode as anode for a high-performance sodium-ion batteries(SIBs),which could especially offer an explanation of Na^(+)storage and solid-electrolyte interface(SEI)stability to the electrochemical performance.展开更多
Perovskite oxides are highly promising catalysts for the combustion removal of volatile organic compounds(VOCs)due to their excellent stability,structural flexibility,and compositional versatility.This study presents ...Perovskite oxides are highly promising catalysts for the combustion removal of volatile organic compounds(VOCs)due to their excellent stability,structural flexibility,and compositional versatility.This study presents a novel perovskite oxide that exhibits enhanced catalytic activity and superior durability for toluene combustion at reduced temperatures.This improvement is achieved by phosphorus doping at the B-site of LaCoO_(3-δ)(LC)perovskite oxide,followed by post-synthesis acid etching for a proper time.The resulting catalyst demonstrates increased specific surface area,higher total pore volume,and enhanced oxygen vacancy concentration both in the bulk and on the surface.Additionally,the activity of surface lattice oxygen species is significantly improved,leading to enhanced catalytic performance in toluene combustion.Notably,the optimized catalyst shows an exceptionally low activation energy(E_(a))of 49.3 kJ mol^(-1),with a T90 reduction of over 214℃compared to the phosphorus doped LC and 190℃compared to pristine LC.Phosphorus doping plays a main role in significantly improving the long-term durability,particularly in the presence of CO_(2)and H_(2)O,while acid etching boosts the catalytic activity.This work introduces a rational and innovative strategy for optimizing VOC oxidation by improving the structure and surface chemical states of perovskite catalysts.展开更多
Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic condu...Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.展开更多
Peroxymonosulfate(PMS)-based advanced oxidation processes(AOPs)are an effective way to remove emerging contaminants(ECs)from water.The catalytic process involving PMS is hindered by the suboptimal electron trans-fer e...Peroxymonosulfate(PMS)-based advanced oxidation processes(AOPs)are an effective way to remove emerging contaminants(ECs)from water.The catalytic process involving PMS is hindered by the suboptimal electron trans-fer efficiency of current catalysts,the further application of AOPs technology is limited.Here,it is proposed that the interfacial electric field can be controlled by bor(B)-doped FeNC catalysts,which shows significant advantages in the efficient generation,release and participation of reactive oxygen species(ROS)in the reaction.The super exchange interaction between Fe sites and N and B sites is realized through the directional transfer of electrons in the interfacial electric field,which ensures the high efficiency and stability of the PMS catalytic process.B doping increases the d orbitals distribution at Fermi level,which facilitates enhanced electron transition activity,thereby promoting the effective generation of (1)^O_(2).At the same time,orbital hybridization causes the center of the d band to move to a lower energy level,which not only contributes to the desorption process of (1)^O_(2),but also accelerates its release.In addition,B-doping also improved the adsorption capacity of organic pollutants and shortened the migration distance of ROS,thereby significantly improving the degradation efficiency of ECs.The B-doping strategy outlined offers a novel approach to the development of FeNC catalysts,it lays a theoretical foundation and offers technical insights for the integration of PMS/AOPs technology in the ECs management.展开更多
Seawater electrolysis is an appealing route toward sustainable hydrogen production,yet its practical deployment is hindered by severe chloride-induced corrosion and parasitic chlorine oxidation.Here,we report noble me...Seawater electrolysis is an appealing route toward sustainable hydrogen production,yet its practical deployment is hindered by severe chloride-induced corrosion and parasitic chlorine oxidation.Here,we report noble metal-doped NiV layered double hydroxides(LDHs)that integrate electronic modulation with a dual chloride confinement mechanism.Ir incorporation simultaneously establishes strong Ir-Cl coordination and dynamically regenerated VO_(4)^(3-)layers,producing an adaptive electrostatic shield that effectively suppresses chloride penetration.As a result,Ir-NiV LDH delivers nearly 100%oxygen evolution reaction selectivity and outstanding stability over2750 h at 500 mA cm^(-2).Meanwhile,Ru doping optimizes the hydrogen evolution pathway,enabling a low overpotential of 195 mV and>2350 h durability.When paired in a twso-electrode electrolyzer,the Ru-NiVLDH‖Ir-NiVLDH system exhibits industrial-level performance and unprecedented robustness in alkaline seawater.This dual chloride confinement concept provides a general framework for catalyst design in corrosive ionic environments,extending beyond seawater splitting toward other electrochemical energy conversion processes.展开更多
An in-built N^(+)pocket electrically doped tunnel field-effect transistor(ED-TFET)-based biosensor has been reported for the first time.The proposed device begins with a PN junction structure with a control gate(CG)an...An in-built N^(+)pocket electrically doped tunnel field-effect transistor(ED-TFET)-based biosensor has been reported for the first time.The proposed device begins with a PN junction structure with a control gate(CG)and two polarity gates(PG1 and PG2).Utilizing the polarity bias concept,a narrow N^(+)pocket is formed between the source and channel without the need for additional doping steps,achieved through biasing PG1 and PG2 at-1.2 V and 1.2 V,respectively.This method not only addresses issues related to doping control but also eliminates constraints associated with thermal budgets and simplifies the fabrication process compared to traditional TFETs.To facilitate biomolecule sensing within the device,a nanogap cavity is formed in the gate dielectric by selectively etching a section of the polarity gate dielectric layer toward the source side.The investigation into the presence of neutral and charged molecules within the cavities has been conducted by examining variations in the electrical properties of the proposed biosensor.Key characteristics assessed include drain current,energy band,and electric field distribution.The performance of the biosensor is measured using various metrics such as drain current(I_(DS)),subthreshold swing(SS),threshold voltage(V_(TH)),drain current ratio(I_(ON)/I_(OFF)).The proposed in-built N^(+)pocket ED-TFET-based biosensor reaches a peak sensitivity of 1.08×10~(13)for a neutral biomolecule in a completely filled nanogap with a dielectric constant of 12.Additionally,the effects of cavity geometry and different fill factors(FFs)on sensitivity are studied.展开更多
The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batte...The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batteries.However,its poor cycling,owing to highpressure phase transitions,is one of its disadvantages.In this study,Cu/Ti was introduced into NFM111 cathode material using a solidphase method.Through both theoretically and experimentally,this study found that Cu doping provides a higher redox potential in NFM111,improving its reversible capacity and charge compensation process.The introduction of Ti would enhance the cycling stability of the material,smooth its charge and discharge curves,and suppress its high-voltage phase transitions.Accordingly,the NaNi_(0.27)Fe_(0.28)Mn_(0.33)Cu_(0.05)Ti_(0.06)O_(2)sample used in the study exhibited a remarkable rate performance of 142.97 mAh·g^(-1)at 0.1 C(2.0-4.2 V)and an excellent capacity retention of 72.81%after 300 cycles at 1C(1C=150 mA·g^(-1)).展开更多
MnO_(2) stands out among cathode materials for aqueous zinc-ion batteries(AZIBs)high capacity and voltage,it has poor stability and slow Zn^(2+) kinetics.Herein,we propose a dual-regulation strategy integrating copper...MnO_(2) stands out among cathode materials for aqueous zinc-ion batteries(AZIBs)high capacity and voltage,it has poor stability and slow Zn^(2+) kinetics.Herein,we propose a dual-regulation strategy integrating copper doping and carbon-based confinement.Residual carbon(RC),derived from acid-washed coal gasification fine slag(CGFS),serves as a conductive and porous framework for the directional growth of Cu-doped MnO_(2) nanowires(CMO@RC).The synergistic modulation of Cu-induced electronic structure tuning and carbon confinement induced mechanical/electrical stabilization significantly enhances Zn^(2+) transport and electrochemical performance.CMO@RC achieves a high capacity of 563 mA·h·g^(−1) at 0.1 A·g^(−1) and maintains 106%after 1000 cycles at 1 A·g^(−1).Kinetic analyses confirm the dual-path Zn^(2+) diffusion and accelerated reaction kinetics,while DFT calculations reveal that Cu doping enhances Mn 3d orbital hybridization and electron interaction with carbon,elevating the density of states near the Fermi level and reducing charge transfer barriers.Furthermore,pouch cell testing demonstrates outstanding flexibility and mechanical resilience.This study provides a cost-effective and scalable strategy for high-performance AZIBs,leveraging both experimental and theoretical validations.展开更多
This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0...This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.展开更多
O3-types layered cathode materials in sodium-ion batteries(SIBs)suffer from the obvious lattice distortion induced by the complex phase transitions during Na^(+)intercalation/deintercalation process,leading to severe ...O3-types layered cathode materials in sodium-ion batteries(SIBs)suffer from the obvious lattice distortion induced by the complex phase transitions during Na^(+)intercalation/deintercalation process,leading to severe structural collapse and performance degradation.Herein,a series of high valence tantalum(Ta^(5+))doped Na(Ni_(0.4)Fe_(0.2)Mn_(0.4))_(1−x)Ta_(x)O_(2)(x=0/0.0025/0.005/0.01)secondary spherical particles are firstly developed,where Ta^(5+)doping enables the refined primary grain with a tightly stacked rod-like morphology.Comprehensive structural analysis via Neutron powder diffraction(NPD)and Synchrotron radiation X-ray diffraction(SXRD)reveals an expanded NaO_(2)slab and a reduction in Na site vacancy.The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy(XAS)and X-ray photoelectron spectroscopy(XPS),unveiling a partial reduction from Ni^(3+)to Ni^(2+)with Ta^(5+)doping.In situ X-ray diffraction(in situ XRD)suggests that the decorated sample undergoes a volume change as low as 0.8%,in contrast with the pristine one(1.5%).Thus,the optimized sample with x=0.005 retains an enhanced capacity retention up to 70.4%at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg^(-1)(0.1 C)and with a good capacity retention of 81.0%at 1 C after 200 cycles in full-cell.Our findings provide new insights into the mechanism of high valence Ta^(5+)doping in stabilizing layered oxides cathode materials for SIBs.展开更多
Modifying the chemical surrounding of N-doped carbon supported single-atom catalysts(SA/NCs)through heteroatom doping is a mainstream approach to optimize their performance for electrocatalytic CO_(2) reduction reacti...Modifying the chemical surrounding of N-doped carbon supported single-atom catalysts(SA/NCs)through heteroatom doping is a mainstream approach to optimize their performance for electrocatalytic CO_(2) reduction reaction.However,conventional SA/NCs mainly consists of in-plane metal sites feature with tightly symmetrical M–N_(4) coordination environments,limiting the regulatory strength of heteroatom doping.Herein,we proposed an edge-assisted heteroatom doping regulation strategy by constructing edge-type Ni sites supported on a hollow and leaf-shaped P-doped NC substrate(eNi/H-NPC).The two-dimensional leaf-shaped and hollow carbon can expose enriched edges.The edge structure can promote the accessibility of active sites,more importantly,intensifies electronic perturbation induced by heteroatom doping.Resultantly,the charge symmetry distribution of Ni–N_4 site is significantly disrupted,and energy barrier associated with the formation of*COOH intermediate is further diminished.eNi/HNPC achieves CO faradaic efficiency(FE_(CO))near 100%at-0.6 V versus reversible hydrogen electrode(vs.RHE)and maintains FE_(CO)over 90%from-0.6 to-1.1 V(vs.RHE)in H-type cells.Remarkably,in gas-diffusion flow cells,eNi/H-NPC exhibits FE_(CO)reaches 98.9%and 96.5%in neutral and acidic electrolytes with the CO current density reach 283.5,and 397.2 mA cm^(-2),respectively,which are much superior than that of the bulk material with dominant in-plane active sites.Moreover,eNi/H-NPC serves as an efficient cathode in Zn–CO_(2) batteries,realized a discharge power density of 4.1 mW cm^(-2),and exceptional cycling durability over 35 h.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demons...Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.展开更多
The efficient electrocatalytic oxidation of glycerol(GLY)is one of the most promising routes for the valorization of GLY.Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver n...The efficient electrocatalytic oxidation of glycerol(GLY)is one of the most promising routes for the valorization of GLY.Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver nanoclusters(Ag NCs),yet the effects of doping mode(surface vs.core)and the interface environment(e.g.,electrolyte concentration)on the electrocatalytic performance for Ag NCs toward GLY oxidation remain understood.In this work,surface-doped Ag_(4)M_(2)(SR)_(8) and core-doped Ag_(24)M(SR)_(18)(M=Ni,Pd,Pt;SR=SPhMe_(2))NCs were synthesized for electrocatalytic GLY oxidation.The results revealed a strong dependence of selectivity on doping mode and electrolyte concentration:under low KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs exhibited 100%selectivity toward oxalic acid(OA),whereas Pd-and Pt-doped Ag_(24)M NCs delivered>95%selectivity for formic acid(FA).In contrast,under high KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs gave rise to>80%FA,while Pd-and Pt-doped Ag_(24)M NCs produced>45%FA.Mechanism studies indicated that Ni doping predominantly enhanced catalytic activity via lowering the activation barrier of the initial reaction step(GLY→glyceraldehyde),whereas Pd and Pt doping modulated selectivity through reducing the energy barrier of the selective branch step(glyceric acid→OA,OA→FA).High KOH concentration promoted the oxidation by increasing the electrochemical active surface area and facilitating electron transfer of Ag NCs.This study provides clear guidance for designing high-performance Ag-based electrocatalysts for biomass valorization.展开更多
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.22178148 and 22278193)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘As a catalyst of the air cathode in zinc-air batteries,tungstic acid ferrous(FeWO_(4)),a nanoscale transition metal tungstate,shows a broad application prospect in the oxygen reduction reaction(ORR).While FeWO_(4)possesses favorable electrochemical properties and thermodynamic stability,its intrinsic semiconductor characteristics result in a relatively slow electron transfer rate,limiting the ORR catalytic activity.In this work,the electronic structure of FeWO_(4)is significantly modulated by introducing phosphorus(P)atoms with abundant valence electrons.The P doping can adjust the electronic structure of FeWO_(4)and then optimize oxygen-containing intermediates'absorption/desorption efficiency to achieve improved ORR activity.Furthermore,the sodium chloride template is utilized to construct a porous carbon framework for anchoring phosphorus-doped iron tungstate(P-FeWO_(4)/PNC).The porous carbon skeleton provides numerous active sites for the absorption/desorption and redox reactions on the P-FeWO_(4)/PNC surface and serves as mass transport channels for reactants and intermediates.The P-FeWO_(4)/PNC demonstrates ORR performance(E1/2=0.86 V vs.RHE).Furthermore,the zinc-air batteries incorporating the P-FeWO_(4)/PNC composite demonstrate an increased peak power density(172.2 mW·cm^(-2)),high specific capacity(810.1 mAh·g^(-1)),and sustained long-term cycling stability lasting up to 240 h.This research not only contributes to the advancement of cost-effective tungsten-based non-precious metallic ORR catalysts,but also guides their utilization in zinc-air batteries.
文摘Silica aerogel has broad applications in the field of high-temperature thermal insulation due to its low density,low thermal conductivity and high stability.However,its thermal insulation performance deteriorates significantly at elevated temperatures exceeding 600℃,primarily due to the collapse of pore structure.Meanwhile,the shielding capacity of SiO_(2) aerogel to the infrared radiation at high temperature is rather low due to the intrinsic properties of SiO_(2).Herein,a strategy for improving the high-temperature stability and infrared shielding properties of SiO_(2) aerogel via Ca doping was explored.Calcium-doped silica aerogel(CSA)powders were prepared by Sol-Gel,hydrothermal,and ambient pressure drying(APD)techniques using water glass and anhydrous calcium chloride as precursors and trimethylchlorosilane as a hydrophobic modifier.The effects of Ca/Si molar ratio in the precursor and hydrothermal conditions(temperature and pH)on the crystalline properties,microscopic morphology and pore structure of CSAs were investigated.The results show that the Ca/Si molar ratio and hydrothermal treatment have significant effects on the microstructure and heat resistance of CSAs in the temperature range of 400-1000℃.The samples sintered at 1000℃have a high specific surface area of 100.1 m^(2)/g and a pore volume of 0.8705 cm^(3)/g,indicating that the CSA has good heat resistance.One-side insulation tests at temperatures up to 600℃show that the sample with a Ca/Si molar ratio of 1.0 has the best insulation performance,with a cold surface temperature of 450℃,which is 27℃lower than that of the pure silica aerogel.
基金Project supported by the National Natural Science Foundation of China (12174075)the Scientific and Technological Bases and Talents of Guangxi (Guike AD21220016)+1 种基金Guangxi Science and Technology Major Project(AA23073018)the special fund for Guangxi Bagui Scholars。
文摘Mn^(2+)-doped CsPbCl_(3)(Mn^(2+):CsPbCl_(3)) nanocrystals(NCs) have attracted considerable attention due to their unique strong and broad orange-red emission band,presenting promising applications in the field of photoelectric devices.However,pristine Mn^(2+):CsPbCl_(3)NCs commonly suffer from low photoluminescence quantum yield(PL QY) and stability issues.Herein,we introduced europium ions(Eu^(3+))into Mn^(2+):CsPbCl_(3)NCs via the thermal injection synthesis method to obtain high performance Eu^(3+)and Mn^(2+)codoped CsPbCl_(3)(Eu^(3+)/Mn^(2+):CsPbCl_(3)) NCs.The maximum PL QY of the resulting Eu^(3+)/Mn^(2+):CsPbCl_(3)NCs reaches up to 90.92%.It is found that the doping of Eu^(3+)ions significantly reduces the non-radiative recombination caused by high defect states,and improves the energy transfer efficiency from exciton to Mn^(2+),thereby boosting the PL performance.Moreover,doping Eu^(3+)ions notably improves the UV-light and water stability of Mn^(2+):CsPbCl_(3)NCs.We further demonstrate the application versatility of Eu^(3+)/Mn^(2+):CsPbCl_(3)NCs in white light emitting diodes(WLEDs) and optical anticounterfeiting applications.This work provides a valuable perspective for the attainment of high performance Mn^(2+):CsPbCl_(3)NCs and lays a foundation for the codoping of other lanthanide ions to adjust the luminescence properties of Mn^(2+):CsPbCl_(3)NCs.
文摘Herein,antibacterial silver‑doped fluorescent carbon dots(Ag‑CDs)were synthesized through a stepwise hydrothermal method,with polyethyleneimine(PEI),citric acid(CA),and silver nitrate(AgNO3)serving as precursors.The applicability and antimicrobial efficacy of these nanomaterials were systematically investigated for metal ion sensing.Experimental evidence demonstrated that the Ag‑CDs exhibited a pronounced fluorescence quenching response toward ferric ions(Fe^(3+)),enabling their quantitative determination via a linear concentration‑dependent relationship.These Ag‑CDs exhibited significant inhibitory effects on biofilm growth and disruption for both Escherichia coli and Staphylococcus aureus.Mechanism investigations indicate that Ag‑CDs induced the death of Escherichia coli and Pseudomonas aeruginosa by disrupting their bacterial morphology and structure,triggering the generation of intracellular reactive oxygen species(ROS),and impairing their antioxidant defense system.
基金financially supported by the National Natural Science Foundation of China(52271200)Guangdong Basic and Applied Basic Research Foundation(2024A1515010393)USTB MatCom of Beijing Advanced Innovation Center for Materials Genome Engineering。
文摘Electrocatalytic carbon dioxide reduction is a crucial method for addressing energy issues and achieving carbon neutrality.Doping of Cu catalysts represents an effective approach to regulate electrocatalytic carbon dioxide reduction.This review article summarizes the research progress on improving the performance of Cu-based material electrocatalysts through doping regulation.The background,fundamental research,evaluation parameters,and methods for catalyst design,along with their influencing factors,are introduced.Emphasis is placed on the impact of doping with different elements(such as noble metals,transition metals,main-group metals,non-metals,etc.)on the performance of Cu-based catalysts,including the mechanisms for enhancing activity,selectivity,and stability.In-situ characterization techniques have revealed the structural evolution and catalytic mechanisms during the doping process.Mechanistic studies,leveraging the ever-advancing computational capabilities and high-throughput methods,have given rise to typical computational descriptors like volcano plots,free-energy diagrams,and machine-learning-based approaches.These descriptors have become key tools for screening high-efficiency catalysts in various application scenarios of the electrochemical carbon dioxide reduction reaction(CO_(2)RR).This article comprehensively summarizes the current research achievements and looks ahead to the future,indicating that strengthening the combination of theory and experiment and exploring industrial applications are the future research directions,aiming to provide a comprehensive reference for the development of highly efficient doped Cu-based electrocatalysts.
文摘Synthetic dyes,particularly azo dyes,pose significant environmental and health risks due to their persistence,toxicity,and potential carcinogenicity.Zinc oxide(ZnO)is a promising photocatalyst for wastewater remediation,but its wide bandgap and rapid charge recombination limit its practical efficacy.Furthermore,conventional doping methods often rely on hazardous chemical precursors,undermining the sustainability of the overall approach.This review introduces a novel and sustainable paradigm:the utilization of biomass-derived precursors as green reagents for the in-situ synthesis and simultaneous phosphorus-nitrogen(P-N)co-doping of ZnO nanoparticles.We critically analyze how the intrinsic biochemical composition of biomass,rich in P,N,and other heteroatoms,facilitates this one-pot,eco-friendly functionalization.This integrated strategy merges the performance enhancement offered by advanced co-doping,such as extended visible-light absorption and suppressed charge recombination,with the core principles of green chemistry and circular economy.It offers a dual benefit:creating highly effective photocatalysts for the degradation of persistent pollutants and valorizing abundant agricultural or biological waste streams.Our comprehensive evaluation goes beyond description to critically assess the underlying mechanisms,comparative efficacy,scalability challenges,and future research directions of this emerging field.This review underscores the unique contribution of biomass-mediated synthesis to advancing sustainable nanotechnology for environmental applications.
基金supported by the National Natural Science Foundation of China (No.52274304)。
文摘Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction(OER) is crucial for advancing overall water splitting(OWS) systems.In this study,we synthesized the electrode material Ce-NiCo-LDHs@SnO_(2)/NF through a two-step hydrothermal reaction,where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO_(2) layer.Ce doping adjusts the internal electronic distribution of Ni Co-LDHs,while the introduction of the SnO_(2) layer enhances electron transfer capability.Together,these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism(LOM).Consequently,Ce-NiCo-LDHs@SnO_(2)/NF exhibits high level electrochemical performance in OER,requiring only 234 m V overpotential to achieve a current density of 10 m A/cm^(2),with a Tafel slope of just 27.39 m V/dec.When paired with Pt/C/NF,an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 m A/cm^(2).Furthermore,the catalyst demonstrates stability for 100 h during the OWS stability test.This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO_(2) layer.
基金supported by National Natural Science Foundation of China(Nos.32271791,32171709 and 22475053)Hunan Provincial Natural Science Foundation of China(No.2024JJ7643)Natural Science Foundation of Shanghai(No.22ZR1404100).
文摘Hard carbon(HC)in sodium-ion batteries is searched by numerous investigations,which can offer the excellent performance of reversible Na^(+)insertion and extraction.The covalent heteroatom doping in HC is recently worth concentrating,which can dilate the interlayer spacing of graphite to adjust the electrochemical storage performance in carbon anodes.However,the reported doping strategies of the modified HC have only resulted in limited improvement,especially unobvious effects on tuning porous structure.In this study,tannin extract and K_(2)SO_(4) are respectively utilized as carbon source and sulfur source for the fabrication of HC,in which K_(2)SO_(4) can contribute to the heteroatom doping,and the pore forming as well.The tannin-derived sulfur-doped carbon anode shows the excellent cycle stability,achieving a high reversible capacity of 520.5 mAh/g at a current density of 100 mA/g.Even after 500 cycles at a current density of 3 A/g,a high specific capacity of 236.7 mAh/g and a capacity retention rate of 92.6%can be reserved.Compared with the initial carbon,the adsorption energy of Na^(+)is multifold times higher,whereas Na^(+)diffusion energy barriers manyfold decrease.Moreover,the full battery assembled with Na_(3)V_(2)(PO_(4))_(3)/tannin-based HC demonstrates a stable cycling performance.This work can manifest the potentiality of the tannin-based electrode as anode for a high-performance sodium-ion batteries(SIBs),which could especially offer an explanation of Na^(+)storage and solid-electrolyte interface(SEI)stability to the electrochemical performance.
基金support from the National Key Research and Development Program of China(Project No.2018YFB1502903).
文摘Perovskite oxides are highly promising catalysts for the combustion removal of volatile organic compounds(VOCs)due to their excellent stability,structural flexibility,and compositional versatility.This study presents a novel perovskite oxide that exhibits enhanced catalytic activity and superior durability for toluene combustion at reduced temperatures.This improvement is achieved by phosphorus doping at the B-site of LaCoO_(3-δ)(LC)perovskite oxide,followed by post-synthesis acid etching for a proper time.The resulting catalyst demonstrates increased specific surface area,higher total pore volume,and enhanced oxygen vacancy concentration both in the bulk and on the surface.Additionally,the activity of surface lattice oxygen species is significantly improved,leading to enhanced catalytic performance in toluene combustion.Notably,the optimized catalyst shows an exceptionally low activation energy(E_(a))of 49.3 kJ mol^(-1),with a T90 reduction of over 214℃compared to the phosphorus doped LC and 190℃compared to pristine LC.Phosphorus doping plays a main role in significantly improving the long-term durability,particularly in the presence of CO_(2)and H_(2)O,while acid etching boosts the catalytic activity.This work introduces a rational and innovative strategy for optimizing VOC oxidation by improving the structure and surface chemical states of perovskite catalysts.
基金financially supported by the National Key Research and Development Program(2022YFE0127400)the National Natural Science Foundation of China(52172040,52202041,and U23B2077)+1 种基金Taishan Scholar Project of Shandong Province(tsqn202211086,ts202208832,tsqnz20221118)the Fundamental Research Funds for the Central Universities(23CX06055A).
文摘Micro silicon(mSi)is a promising anode candidate for all-solid-state batteries due to its high specific capacity,low side reactions,and high tap density.However,silicon suffers from its poor electronic and ionic conductivity,which is particularly severe on a micro scale and in solid-state systems,leading to increased polarization and inferior electrochemical performance.Doping can broaden the transmission pathways and reduce the diffusion energy barrier for electrons and lithium ions.However,achieving effective,uniform doping in mSi is challenging due to its longer diffusion paths and higher energy barriers.Therefore,current doping research is primarily limited to nanosilicon.In this study,we successfully used a Joule-heating activated staged thermal treatment to achieve full-depth doping of germanium(Ge)in the mSi substrate.The Joule-heating process activated the mSi substrate,resulting in abundant vacancy defects that reduced the diffusion barrier of Ge into the silicon lattice and facilitated full-depth Ge doping.Surprisingly,the resulting Si-Ge anode exhibited significantly enhanced electrical conductivity(70 times).Meanwhile,the improved Li-ion conductivity in mSi and the reduced Young’s modulus enhance the electrode reaction kinetics and integrity after cycling.Ge-doped silicon anodes demonstrate excellent electrochemical performance when applied in sulfide solid-state half-cells and full-cells.This work provides substantial insights into the rational structural design of mSi alloyed anode materials,paving the way for the development of high-performance solid-state Li-ion batteries.
基金supported by the National Natural Science Foundation of China(No.22278156)the Guangdong Special Support Program Project(No.2021JC060580)+1 种基金the Young Elite Scientists Sponsorship Program by CAST-Doctoral Student Special Plan,the China Scholarship Council Program(No.202406150148)the Natural Science Foundation of Guangdong Province(No.2023A1515011186).
文摘Peroxymonosulfate(PMS)-based advanced oxidation processes(AOPs)are an effective way to remove emerging contaminants(ECs)from water.The catalytic process involving PMS is hindered by the suboptimal electron trans-fer efficiency of current catalysts,the further application of AOPs technology is limited.Here,it is proposed that the interfacial electric field can be controlled by bor(B)-doped FeNC catalysts,which shows significant advantages in the efficient generation,release and participation of reactive oxygen species(ROS)in the reaction.The super exchange interaction between Fe sites and N and B sites is realized through the directional transfer of electrons in the interfacial electric field,which ensures the high efficiency and stability of the PMS catalytic process.B doping increases the d orbitals distribution at Fermi level,which facilitates enhanced electron transition activity,thereby promoting the effective generation of (1)^O_(2).At the same time,orbital hybridization causes the center of the d band to move to a lower energy level,which not only contributes to the desorption process of (1)^O_(2),but also accelerates its release.In addition,B-doping also improved the adsorption capacity of organic pollutants and shortened the migration distance of ROS,thereby significantly improving the degradation efficiency of ECs.The B-doping strategy outlined offers a novel approach to the development of FeNC catalysts,it lays a theoretical foundation and offers technical insights for the integration of PMS/AOPs technology in the ECs management.
基金supported by the National Natural Science Foundation of China(No.22209115,52472226,and U23A20573)the Key Research and Development Program of Shandong Province(No.2022CXGC010305)+2 种基金Guangdong Basic and Applied Basic Research Foundation(No.2025A1515011809,2023B1515120022 and 2022B1515120001)Shenzhen Science and Technology Innovation Program(No.RCBS20231211090522040,KJZD20240903095610014,and KJZD20240903095712017)the High-Level Professional Team in Shenzhen(KQTD20210811090045006)。
文摘Seawater electrolysis is an appealing route toward sustainable hydrogen production,yet its practical deployment is hindered by severe chloride-induced corrosion and parasitic chlorine oxidation.Here,we report noble metal-doped NiV layered double hydroxides(LDHs)that integrate electronic modulation with a dual chloride confinement mechanism.Ir incorporation simultaneously establishes strong Ir-Cl coordination and dynamically regenerated VO_(4)^(3-)layers,producing an adaptive electrostatic shield that effectively suppresses chloride penetration.As a result,Ir-NiV LDH delivers nearly 100%oxygen evolution reaction selectivity and outstanding stability over2750 h at 500 mA cm^(-2).Meanwhile,Ru doping optimizes the hydrogen evolution pathway,enabling a low overpotential of 195 mV and>2350 h durability.When paired in a twso-electrode electrolyzer,the Ru-NiVLDH‖Ir-NiVLDH system exhibits industrial-level performance and unprecedented robustness in alkaline seawater.This dual chloride confinement concept provides a general framework for catalyst design in corrosive ionic environments,extending beyond seawater splitting toward other electrochemical energy conversion processes.
基金Project supported by the Ministry of Education’s Supply and Demand Matching Employment and Education Project(Grant No.2024110776329)。
文摘An in-built N^(+)pocket electrically doped tunnel field-effect transistor(ED-TFET)-based biosensor has been reported for the first time.The proposed device begins with a PN junction structure with a control gate(CG)and two polarity gates(PG1 and PG2).Utilizing the polarity bias concept,a narrow N^(+)pocket is formed between the source and channel without the need for additional doping steps,achieved through biasing PG1 and PG2 at-1.2 V and 1.2 V,respectively.This method not only addresses issues related to doping control but also eliminates constraints associated with thermal budgets and simplifies the fabrication process compared to traditional TFETs.To facilitate biomolecule sensing within the device,a nanogap cavity is formed in the gate dielectric by selectively etching a section of the polarity gate dielectric layer toward the source side.The investigation into the presence of neutral and charged molecules within the cavities has been conducted by examining variations in the electrical properties of the proposed biosensor.Key characteristics assessed include drain current,energy band,and electric field distribution.The performance of the biosensor is measured using various metrics such as drain current(I_(DS)),subthreshold swing(SS),threshold voltage(V_(TH)),drain current ratio(I_(ON)/I_(OFF)).The proposed in-built N^(+)pocket ED-TFET-based biosensor reaches a peak sensitivity of 1.08×10~(13)for a neutral biomolecule in a completely filled nanogap with a dielectric constant of 12.Additionally,the effects of cavity geometry and different fill factors(FFs)on sensitivity are studied.
基金supported by the Low-Cost Long-Life Batteries program,China(No.WL-24-08-01)the National Natural Science Foundation of China(No.22279007)。
文摘The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batteries.However,its poor cycling,owing to highpressure phase transitions,is one of its disadvantages.In this study,Cu/Ti was introduced into NFM111 cathode material using a solidphase method.Through both theoretically and experimentally,this study found that Cu doping provides a higher redox potential in NFM111,improving its reversible capacity and charge compensation process.The introduction of Ti would enhance the cycling stability of the material,smooth its charge and discharge curves,and suppress its high-voltage phase transitions.Accordingly,the NaNi_(0.27)Fe_(0.28)Mn_(0.33)Cu_(0.05)Ti_(0.06)O_(2)sample used in the study exhibited a remarkable rate performance of 142.97 mAh·g^(-1)at 0.1 C(2.0-4.2 V)and an excellent capacity retention of 72.81%after 300 cycles at 1C(1C=150 mA·g^(-1)).
基金support from the Key projects of scientific research projects of universities in Anhui Province(2024AH050360).
文摘MnO_(2) stands out among cathode materials for aqueous zinc-ion batteries(AZIBs)high capacity and voltage,it has poor stability and slow Zn^(2+) kinetics.Herein,we propose a dual-regulation strategy integrating copper doping and carbon-based confinement.Residual carbon(RC),derived from acid-washed coal gasification fine slag(CGFS),serves as a conductive and porous framework for the directional growth of Cu-doped MnO_(2) nanowires(CMO@RC).The synergistic modulation of Cu-induced electronic structure tuning and carbon confinement induced mechanical/electrical stabilization significantly enhances Zn^(2+) transport and electrochemical performance.CMO@RC achieves a high capacity of 563 mA·h·g^(−1) at 0.1 A·g^(−1) and maintains 106%after 1000 cycles at 1 A·g^(−1).Kinetic analyses confirm the dual-path Zn^(2+) diffusion and accelerated reaction kinetics,while DFT calculations reveal that Cu doping enhances Mn 3d orbital hybridization and electron interaction with carbon,elevating the density of states near the Fermi level and reducing charge transfer barriers.Furthermore,pouch cell testing demonstrates outstanding flexibility and mechanical resilience.This study provides a cost-effective and scalable strategy for high-performance AZIBs,leveraging both experimental and theoretical validations.
基金financially supported by the National Natural Science Foundation of China(No.22309067)the Open Project Program of the State Key Laboratory of Materials-Oriented Chemical Engineering,China(No.KL21-05)the Marine Equipment and Technology Institute,Jiangsu University of Science and Technology,China(No.XTCX202404)。
文摘This study focused on improving the cathode performance of Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.15)O_(3-δ)(BSCN)-based perovskite materials through molybdenum(Mo)doping.Pure BSCN and Mo-modified-BSCN—Ea_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.1)Mo_(0.05)O_(3-δ)(B S CNM_(0.05)),Ba_(0.6)Sr_(0.4)Co_(0.85)Nb_(0.05)Mo_(0.1)O_(3-δ)(BSCNM_(0.1)),and Ba_(0.6)Sr_(0.4)Co_(0.85)Mo_(0.15)O_(3-δ)(BSCM)—with Mo doping contents of 5mol%,10mol%,and15mol%,respectively,were successfully prepared using the sol-gel method.The effects of Mo doping on the crystal structure,conductivity,thermal expansion coefficient,oxygen reduction reaction(ORR)activity,and electrochemical performance were systematically evaluated using X-ray diffraction analysis,thermally induced characterization,electrochemical impedance spectroscopy,and single-cell performance tests.The results revealed that Mo doping could improve the conductivity of the materials,suppress their thermal expansion effects,and significantly improve the electrochemical performance.Surface chemical state analysis using X-ray photoelectron spectroscopy revealed that 5mol%Mo doping could facilitate a high adsorbed oxygen concentration leading to enhanced ORR activity in the materials.Density functional theory calculations confirmed that Mo doping promoted the ORR activity in the materials.At an operating temperature of 600℃,the BSCNM_(0.05)cathode material exhibited significantly enhanced electrochemical impedance characteristics,with a reduced area specific resistance of 0.048Ω·cm~2,which was lower than that of the undoped BSCN matrix material by 32.39%.At the same operating temperature,an anode-supported single cell using a BSCNM_(0.05)cathode achieved a peak power density of 1477 mW·cm^(-2),which was 30.71%,56.30%,and 171.50%higher than those of BSCN,BSCNM_(0.1),and B SCM,respectively.The improved ORR activity and electrochemical performance of BSCNM_(0.05)indicate that it can be used as a cathode material in low-temperature solid oxide fuel cells.
基金supported by the National Natural Science Foundation of China (52402298, 52172224, 52202228, 22479112)the Science and Technology Correspondent Project of Tianjin(24YDTPJC00240)+3 种基金Science Research Project of Hebei Education Department (BJK2022011)Central Funds Guiding the Local Science and Technology Development of Hebei Province (236Z4404G)the Beijing Tianjin Hebei Basic Research Cooperation Special Project(E2024202273)Tianjin Sci.&Tech. Program (22YFYSHZ00220)
文摘O3-types layered cathode materials in sodium-ion batteries(SIBs)suffer from the obvious lattice distortion induced by the complex phase transitions during Na^(+)intercalation/deintercalation process,leading to severe structural collapse and performance degradation.Herein,a series of high valence tantalum(Ta^(5+))doped Na(Ni_(0.4)Fe_(0.2)Mn_(0.4))_(1−x)Ta_(x)O_(2)(x=0/0.0025/0.005/0.01)secondary spherical particles are firstly developed,where Ta^(5+)doping enables the refined primary grain with a tightly stacked rod-like morphology.Comprehensive structural analysis via Neutron powder diffraction(NPD)and Synchrotron radiation X-ray diffraction(SXRD)reveals an expanded NaO_(2)slab and a reduction in Na site vacancy.The potential charge compensation mechanism is further illustrated by X-ray absorption spectroscopy(XAS)and X-ray photoelectron spectroscopy(XPS),unveiling a partial reduction from Ni^(3+)to Ni^(2+)with Ta^(5+)doping.In situ X-ray diffraction(in situ XRD)suggests that the decorated sample undergoes a volume change as low as 0.8%,in contrast with the pristine one(1.5%).Thus,the optimized sample with x=0.005 retains an enhanced capacity retention up to 70.4%at 1 C after 300 cycles in half-cell and delivers a high energy density of 251 Wh kg^(-1)(0.1 C)and with a good capacity retention of 81.0%at 1 C after 200 cycles in full-cell.Our findings provide new insights into the mechanism of high valence Ta^(5+)doping in stabilizing layered oxides cathode materials for SIBs.
基金supported by Basic and Applied Basic Research Foundation of Guangdong province(2024A1515110016 and2023A1515140020)National Natural Science Foundation of China(52070042,and 52300127)。
文摘Modifying the chemical surrounding of N-doped carbon supported single-atom catalysts(SA/NCs)through heteroatom doping is a mainstream approach to optimize their performance for electrocatalytic CO_(2) reduction reaction.However,conventional SA/NCs mainly consists of in-plane metal sites feature with tightly symmetrical M–N_(4) coordination environments,limiting the regulatory strength of heteroatom doping.Herein,we proposed an edge-assisted heteroatom doping regulation strategy by constructing edge-type Ni sites supported on a hollow and leaf-shaped P-doped NC substrate(eNi/H-NPC).The two-dimensional leaf-shaped and hollow carbon can expose enriched edges.The edge structure can promote the accessibility of active sites,more importantly,intensifies electronic perturbation induced by heteroatom doping.Resultantly,the charge symmetry distribution of Ni–N_4 site is significantly disrupted,and energy barrier associated with the formation of*COOH intermediate is further diminished.eNi/HNPC achieves CO faradaic efficiency(FE_(CO))near 100%at-0.6 V versus reversible hydrogen electrode(vs.RHE)and maintains FE_(CO)over 90%from-0.6 to-1.1 V(vs.RHE)in H-type cells.Remarkably,in gas-diffusion flow cells,eNi/H-NPC exhibits FE_(CO)reaches 98.9%and 96.5%in neutral and acidic electrolytes with the CO current density reach 283.5,and 397.2 mA cm^(-2),respectively,which are much superior than that of the bulk material with dominant in-plane active sites.Moreover,eNi/H-NPC serves as an efficient cathode in Zn–CO_(2) batteries,realized a discharge power density of 4.1 mW cm^(-2),and exceptional cycling durability over 35 h.
基金financially supported by the Natural Science Foundation of Shandong Province (No.ZR2022QE076)the National Natural Science Foundation of China (No.52202092)the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China (No.2023KJ104)。
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR) into valuable formate provides a strategy for carbon neutrality.Bismuth(Bi) catalysts,attributed to their appropriate energy barrier of OCHO*intermediate,have demonstrated substantial potential for the advancement of electrocatalytic CO_(2) reduction to formate.However,due to the weak bonding of protons(H^(*)) of Bi,the available protonate of CO_(2) on Bi is insufficient,which limits the formation of OCHO^(*).Prediction by theoretical calculation,chlorine doping can effectively promote the dissociation of H_(2)O and thus achieve effective proton supply.We prepare chlorine-doped Bi(Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO_(2) .An obvious improvement of faradaic efficiency(FE) of formate(96.7% at-0.95 V vs.RHE) can be achieved on Cl-Bi,higher than that of Bi(89.4%).Meanwhile,Cl-Bi has the highest formate production rate of 275 μmol h^(-1)cm^(-2)at-0.95 V vs.RHE,which is 1.2 times higher than that of Bi(224 μmol h^(-1)cm^(-2)).In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H_(2)O and supply sufficient protons to promote the protonation of CO_(2) to OCHO^(*),which is consistent with theoretical calculation.The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
基金support from the Jiangsu Natural Science Foundation of China(BK20230329)the National Natural Science Foundation of China(22401147,22361132540,and 22178161)the Russian Science Foundation(23-73-30007).
文摘The efficient electrocatalytic oxidation of glycerol(GLY)is one of the most promising routes for the valorization of GLY.Doping has emerged as a powerful strategy to tailor the electrocatalytic performance of silver nanoclusters(Ag NCs),yet the effects of doping mode(surface vs.core)and the interface environment(e.g.,electrolyte concentration)on the electrocatalytic performance for Ag NCs toward GLY oxidation remain understood.In this work,surface-doped Ag_(4)M_(2)(SR)_(8) and core-doped Ag_(24)M(SR)_(18)(M=Ni,Pd,Pt;SR=SPhMe_(2))NCs were synthesized for electrocatalytic GLY oxidation.The results revealed a strong dependence of selectivity on doping mode and electrolyte concentration:under low KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs exhibited 100%selectivity toward oxalic acid(OA),whereas Pd-and Pt-doped Ag_(24)M NCs delivered>95%selectivity for formic acid(FA).In contrast,under high KOH concentration,Pd-and Pt-doped Ag_(4)M_(2) NCs gave rise to>80%FA,while Pd-and Pt-doped Ag_(24)M NCs produced>45%FA.Mechanism studies indicated that Ni doping predominantly enhanced catalytic activity via lowering the activation barrier of the initial reaction step(GLY→glyceraldehyde),whereas Pd and Pt doping modulated selectivity through reducing the energy barrier of the selective branch step(glyceric acid→OA,OA→FA).High KOH concentration promoted the oxidation by increasing the electrochemical active surface area and facilitating electron transfer of Ag NCs.This study provides clear guidance for designing high-performance Ag-based electrocatalysts for biomass valorization.
