Structural engineering of Fe single-atom oxygen reduction catalyst with high site density and improved mass transfer

Fe-N-C catalysts are widely considered as promising non-precious-metal candidates for electrocatalytic oxygen reduction reaction(ORR),Yet despite their high catalytic activity through rational modulation,challenges remain in their low site density and unsatisfactory mass transfer structure.Herein,we present a structural engineering approach employing a soft-template coating strategy to fabricate a hollow and hierarchically porous N-doped carbon framework anchored with atomically dispersed Fe sites(FeNCh) as an efficient ORR catalyst.The combination of hierarchical porosity and high exterior surface area is proven crucial for exposing more active sites,which gives rise to a remarkable ORR performance with a half-wave potential of 0.902 V in 0.1 m KOH and 0.814 V in 0.1 m HClO_(4),significantly outperforming its counterpart with solid structure and dominance of micropores(FeNC-s).The mass transfer property is revealed by in-situ electrochemical impedance spectroscopy(EIS) measurement.The distribution of relaxation time(DRT) analysis is further introduced to deconvolve the kinetic and mass transport processes,which demonstrates an alleviated mass transport resistance for FeNC-h,validating the effectiveness of structural engineering.This work not only provides an effective structural engineering approach but also contributes to the comprehensive mass transfer evaluation on advanced electrocatalyst for energy conversion applications.

Surface structural engineering of carbonyl iron powder for enhancing microwave absorption and anti-oxidation performance

Surface structural engineering is desirable in modifying the surface performance of carbonyl iron powder(CIP)to enhance microwave absorption(MA)and anti-oxidation performance.Herein,the surface shape-dependent CIP absorbers are designed via surface coating with zinc oxide(ZnO)nanoparticles and then a thermal annealing treatment.The morphology of ZnO nanoparticles which can be easily regulated by controlling the annealing temperature ultimately affects the MA performance of CIP coating with ZnO nanoparticles(CIP@ZnO).The core-shell CIP@ZnO particles with cubic cone ZnO nanoparticles exhibit ex-cellent MA performance and thermal stability in comparison to the original CIP.Specifically,the CIP@ZnO annealed at 350 ℃(CIP@ZnO-350)samples which have the cubic cone ZnO nanoparticles exhibit a min-imum reflection loss(RLmin)of-55.35 dB at a thickness of 2.1 mm and a maximum effective absorp-tion bandwidth(EAB)of 7.09 GHz at a thickness of 2.0 mm.In addition,the antioxidant property of the CIP@ZnO composite particles is abruptly enhanced,which breaks the restriction of the application of CIP at high temperatures.The superior MA performance of CIP@ZnO particles with cubic cone ZnO nanoparti-cles comes from the enhancement in surface shape-dependent multiple microwave scattering,interfacial polarization,and electromagnetic-dielectric synergism between ZnO and CIP.

Heteroatom Structural Engineering Enables Ethenylene-Bridged Bisisoindigo-Based Copolymers to Exhibit Unique n-Type Transistor Performance

Herein,we report three novel electron-deficient aromatics,ethenylene-bridged bisisoindigos 3,3′-((3E,3′E)-((E)-ethene-1,2-diyl)bis(1-(4-decyltetradecyl)-2-oxoind-oline-6-yl-3-ylidene))bis(1-(4-decyltetradecyl)-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one)(NCCN),3,3′-((3E,3′E)-((E)-ethene-1,2-diyl)bis(1-(4-decyltetradecyl)-7-fluoro-2-oxoindoline-6-yl-3-ylidene))bis(1-(4-decyltetradecyl)-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one)(NFFN),and(3E,3″E)-6,6″-((E)-ethene-1,2-diyl)bis(1,1′-bis(4-decyltetradecyl)-[3,3′-bipyrrolo[2,3-b]pyridinylidene]-2,2′(1H,1′H)-dione)(NNNN),and their derived donor–acceptor(D–A)copolymers,namely poly[3,3′-((3E,3′E)-((E)-ethene-1,2-diyl)bis(1-(4-decyltetradecyl)-2-oxoindoline-6-yl-3-ylidene))bis(1-(4-decyltetradecyl)-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one-6-yl)]-alt-[5,6-difluoro-4,7-di[(thiophen-2-yl)-5-yl)]benzo[c][1,2,5]thiadiazole](PNCCN-FBT),poly[3,3′-((3E,3′E)-((E)-ethene-1,2-diyl)bis(1-(4-decyltetradecyl)-7-fluoro-2-oxoindoline-6-yl-3-ylidene))bis(1-(4-decyltetradecyl)-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one-6-yl)]-alt-[5,6-difluoro-4,7-di[(thiophen-2-yl)-5-yl)]benzo[c][1,2,5]thiadiazole](PNFFNFBT),and poly[(3E,3″E)-6′,6‴-((E)-ethene-1,2-diyl)bis(1,1′-bis(4-decyltetradecyl)-[3,3′-bipyrrolo[2,3-b]pyridinylidene]-2,2′(1H,1′H)-dione-6-yl)]-alt-[5,6-difluoro-4,7-di[(thiophen-2-yl)-5-yl)]benzo[c][1,2,5]thiadiazole](PNNNN-FBT),in which 5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole(FBT)acts as the electron-donating units.The ethenylene-bridging unit reduces the steric hindrance of the three bisisoindigos.Incorporation of heteroatoms,such as fluorine and sp2-nitrogen atoms,endows them with multiple CH···F,CH···N,and N···S intramolecular hydrogen bonds/nonbinding interactions,resulting in increasing backbone planarity from NCCN,NFFN,to NNNN,and thus from PNCCN-FBT,PNFFN-FBT,to PNNNN-FBT.We found that all copolymers formed an improved molecular packing in the 1-chloronaphthalene(CN)-processed thin film compared with the 1,2-dichlorobenzene-processed one.The CN-processed PNCCN-FBT-based polymer field-effect transistors showed ambipolar transport characteristics with the electron mobility(μe)and hole mobility of 1.20 and 0.46 cm^(2)V^(−1)^s(−1),respectively,while the PNFFN-FBT-and PNNNN-FBT-based ones afforded unique n-type transport characteristics with impressively highμe up to 3.28 cm^(2)V^(−1)^s(−1).The lower frontier molecular orbital energy levels of PNFFN-FBT are the key reason for its higherμe.This study demonstrated that heteroatom structural engineering on ethenylene-bridged bisisoindigos is an effective way to construct high-performance n-type polymer semiconductors.

Multiscale structural engineering of carbon nitride for enhanced photocatalytic H2O2 production

Carbon nitride(C_(3)N_(4))holds great promise for photocatalytic H_(2)O_(2)production from oxygen reduction.In spite of great research efforts,they still suffer from low catalytic efficiency primarily limited by the fast recombination of photogenerated charge carriers.In this work,we report the multiscale structural engineering of C_(3)N_(4)to significantly improve its optoelectronic properties and consequently photocatalytic performance.The product consists of porous spheres with high surface areas,abundant nitrogen defects,and alkali metal doping.Under visible light irradiation,our catalyst shows a remarkable H_(2)O_(2)production rate of 3,080μmol·g^(−1)·h^(−1),which is more than 10 times higher than that of bulk C_(3)N_(4)and exceeds those of most other C_(3)N_(4)-based photocatalysts.Moreover,the catalyst exhibits great stability,and can continuously work for 15 h without obvious activity decay under visible light irradiation,eventually giving rise to a high H_(2)O_(2)concentration of ca.45 mM.

From VIB‑to VB‑Group Transition Metal Disulfides:Structure Engineering Modulation for Superior Electromagnetic Wave Absorption

The laminated transition metal disulfides(TMDs),which are well known as typical two-dimensional(2D)semiconductive materials,possess a unique layered structure,leading to their wide-spread applications in various fields,such as catalysis,energy storage,sensing,etc.In recent years,a lot of research work on TMDs based functional materials in the fields of electromagnetic wave absorption(EMA)has been carried out.Therefore,it is of great significance to elaborate the influence of TMDs on EMA in time to speed up the application.In this review,recent advances in the development of electromagnetic wave(EMW)absorbers based on TMDs,ranging from the VIB group to the VB group are summarized.Their compositions,microstructures,electronic properties,and synthesis methods are presented in detail.Particularly,the modulation of structure engineering from the aspects of heterostructures,defects,morphologies and phases are systematically summarized,focusing on optimizing impedance matching and increasing dielectric and magnetic losses in the EMA materials with tunable EMW absorption performance.Milestones as well as the challenges are also identified to guide the design of new TMDs based dielectric EMA materials with high performance.

Synthesis of Reviews on Auscultation, Approaches, and Methods for Engineering Structures

Topometric auscultation is used to monitor the durability of structures, measure deformations linked to the structure of a structure or to the movement of the ground over a part of the globe, set up warning systems, etc. It first appeared as a visual method and rapidly evolved through the various techniques used. Some of these techniques using topography are used in several fields (civil engineering, geodesy, topography, mechanics, nuclear engineering, hydraulics, physics, etc.). These topometric techniques have undergone major changes as a result of technological advances, growing needs in the monitoring of movements or deformations, increased requirements and new challenges. The methodology adopted depends on the measuring instrument used, the parameters to be estimated and access to the area to be measured. There are two types of methods: destructive and non-destructive. In addition to the visual method, they can also be classified as mechanical, physico-chemical, dynamometric, electrophysical and geometric. The estimated parameter varies according to the methodology adopted. It can be defined by coordinates, distances, potential, electrical resistance, etc.

Two-dimensional polymeric carbon nitride: structural engineering for optimizing photocatalysis

As a two-dimensional(2D) material, polymeric carbon nitride(g-C_3N_4) nanosheet holds great potentials in environmental purification and solar energy conversion. In this review, we summarized latest progress in the optimization of photocatalytic performance in 2D g-C_3N_4. Some of the latest structural engineering methods were summed up, where the relevant influences on the behaviors of photoinduced species were emphasized. Furthermore, the construction strategies for band structure modulation and charge separation promotion were then discussed in detail. A brief discussion on the opportunity and challenge of 2D g-C_3N_4-based photocatalysis are presented as the conclusion of this review.

Structural engineering of sulfur-doped carbon encapsulated bismuth sulfide core-shell structure for enhanced potassium storage performance

Owing to the high theoretical capacity,metal sulfides have emerged as promising anode materials for potassium-ion batteries(PIBs).However,sluggish kinetics,drastic volume expansion,and polysulfide dissolution during charge/discharge result in unsatisfactory electrochemical performance.Herein,we design a core-shell structure consisting of an active bismuth sulfide core and a highly conductive sulfur-doped carbon shell(Bi2S3@SC)as a novel anode material for PIBs.Benefiting from its unique core-shell structure,this Bi2S3@SC is endowed with outstanding potassium storage performance with high specific capacity(626 mAh·g^(-1)under 50 mA·g^(-1))and excellent rate capability(268.9 mAh·g^(-1)at 1 A·g^(-1)).More importantly,a Bi2S3@SC//KFe[Fe(CN)6]full cell is successfully fabricated,which achieves a high reversible capacity of 257 mAh·g^(-1)at 50 mA·g^(-1)over 50 cycles,holding great potentials in practical applications.Density functional theory(DFT)calculations reveal that potassium ions have a low diffusion barrier of 0.54 eV in Bi2S3 due to the weak van der Waals interactions between layers.This work heralds a promising strategy in the structural design of high-performance anode materials for PIBs.

Structural engineering of transition-metal nitrides for surfaceenhanced Raman scattering chips

Noble-metal-free surface-enhanced Raman scattering(SERS)substrates have attracted great attention for their abundant sources,good signal uniformity,superior biocompatibility,and high chemical stability.However,the lack of controllable synthesis and fabrication of noble-metal-free substrates with high SERS activity impedes their practical applications.Herein,we propose a general strategy to fabricate a series of planar transition-metal nitride(TMN)SERS chips via an ambient temperature sputtering deposition route.For the first time,tungsten nitride(WN)and tantalum nitride(TaN)are used as SERS materials.These planar TMN chips show remarkable Raman enhancement factors(EFs)with~105 owing to efficient photoinduced charge transfer process between TMN chips and probe molecules.Further,structural engineering of these TMN chips is used to improve their SERS activity.Benefiting from the synergistic effect of charge transfer process and electric field enhancement by constructing a nanocavity structure,the Raman EF of WN nanocavity chips could be greatly improved to~1.29×10^(7),which is an order of magnitude higher than that of planar chips.Moreover,we also design the WN/monolayer MoS2 heterostructure chips.With the increase of surface electron density on the upper WN and more exciton resonance transitions in the heterostructure,a~1.94×10^(7)level EF and a 5×10^(-10)M level detection limit could be achieved.Our results provide important guidance for the structural design of ultrasensitive noble-metal-free SERS chips.

Causality in structural engineering: discovering new knowledge by tying induction and deduction via mapping functions and explainable artificial intelligence

Causality is the science of cause and effect.It is through causality that explanations can be derived,theories can be formed,and new knowledge can be discovered.This paper presents a modern look into establishing causality within structural engineering systems.In this pursuit,this paper starts with a gentle introduction to causality.Then,this paper pivots to contrast commonly adopted methods for inferring causes and effects,i.e.,induction(empiricism)and deduc-tion(rationalism),and outlines how these methods continue to shape our structural engineering philosophy and,by extension,our domain.The bulk of this paper is dedicated to establishing an approach and criteria to tie principles of induction and deduction to derive causal laws(i.e.,mapping functions)through explainable artificial intelligence(XAI)capable of describing new knowledge pertaining to structural engineering phenomena.The proposed approach and criteria are then examined via a case study.

Application of 2-D and 3-D Geo-electrical Resistivity Tomography and Geotechnical Soil Evaluation for Engineering Site Investigation:A Case Study of Okerenkoko Primary School,Warri-Southwest,Delta State,Nigeria

In the design of building structures,joint efforts must be decided to resolve the depth of competent layers across the intended site to safeguard the durability of civil engineering structures and to avert the disastrous consequences of structural failure and collapse.In this study,an integrated methodology that employed DC resistivity tomography involving 2-D and 3-D techniques and geotechnical-soil analysis was used to evaluate subsoil conditions for engineering site investigation at Okerenkoko primary school,in the Warri-southwest area of Delta State,to adduce the phenomena responsible for the visible cracks/structural failure observed in the buildings.The results obtained brought to light the geological structure beneath the subsurface,which consists of four geoelectric layers identified as topsoil,dry/lithified upper sandy layer,wet sand(water-saturated)and peat/clay/sandy clayey soil(highly water-saturated).The deeply-seated peat/clay materials(ρ≤20Ωm)were delineated in the study area to the depths of 17.1 m and 19.8 m from 2-D and 3-D tomography respectively.3-D images presented as horizontal depth slices revealed the dominance of very low resistivity materials i.e.peat/clay/sandy clay within the fourth,fifth and sixth layers at depths ranging from 8.68-12.5 m,12.5-16.9 m and 16.9-21.9 m respectively.The dominance of mechanically unstable peat/clay/sandy clay layers beneath the subsurface,which are highly mobile in response to volumetric changes,is responsible for the noticeable cracks/failure detected on structures within the study site.These observations were validated by a geotechnical test of soil samples in the study area.Atterberg’s limits of the samples revealed plasticity indices of zero.Thus,the soil samples within the depth analyzed were representatives of sandy soil that does not possess any plasticity.The methods justifiably provided relevant information on the subsurface geology beneath the study site and should be appropriated as major tools for engineering site assessment/geotechnical projects.

Performance optimization of chalcogenide catalytic materials in lithium-sulfur batteries:Structural and electronic engineering

Lithium-sulfur batteries(LSBs)boasting remarkable energy density have garnered significant attention within academic and industrial spheres.Nevertheless,the progression of LSBs remains constrained by the languid redox kinetics intrinsic to sulfur and the pronounced shuttle effect induced by lithium polysulfides(Li PSs),which seriously affecting the energy density,cycling life and rate capacity.The conceptualization and implementation of catalytic materials stand acknowledged as a propitious stratagem for orchestrating kinetic modulation,particularly in excavating the conversion of LiPSs and has evolved into a focal point for disposing.Among them,chalcogenide catalytic materials(CCMs)have shown satisfactory catalytic effects ascribe to the unique physicochemical properties,and have been extensively developed in recent years.Considering the lack of systematic summary regarding the development of CCMs and corresponding performance optimization strategies,herein,we initiate a comprehensive review regarding the recent progress of CCMs for effective collaborative immobilization and accelerated transformation kinetics of Li PSs.Following that,the modulation strategies to improve the catalytic activity of CCMs are summarized,including structural engineering(morphology engineering,surface/interface engineering,crystal engineering)and electronic engineering(doping and vacancy,etc.).Finally,the application prospect of CCMs in LSBs is clarified,and some enlightenment is provided for the reasonable design of CCMs serving practical LSBs.

Experimental and computational optimization of Prussian blue analogues as high-performance cathodes for sodium-ion batteries:A review

In this review,we discuss the electrochemical properties of Prussian blue(PB)for Na^(+)storage by combining structural engineering and electrolyte modifications.We integrated experimental data and density functional theory(DFT)in sodium-ion battery(SIB)research to refine the atomic arrangements and crystal lattices and introduce substitutions and dopants.These changes affect the lattice stability,intercalation,electronic and ionic conductivities,and electrochemical performance.We unraveled the intricate structure-electrochemical behavior relationship by combining experimental data with computational models,including first-principles calculations.This holistic approach identified techniques for optimizing PB and Prussian blue analog(PBA)structu ral properties for SIBs.We also discuss the tuning of electrolytes by systematically adjusting their composition,concentration,and additives using a combination of molecular dynamics(MD)simulations and DFT computations.Our review offers a comprehensive assessment of strategies for enhancing the electrochemical properties of PB and PBAs through structural engineering and electrolyte modifications,combining experimental insights with advanced computational simulations,and paving the way for next-generation energy storage systems.

Unleashing the Potential of Unidirectional Mechanical Materials: Breakthroughs and Promising Applications

The emergence of mechanically one-way materials presents an exciting opportunity for materials science and engineering. These substances exhibit unique nonreciprocal mechanical responses, enabling them to selectively channel mechanical energy and facilitate directed sound propagation, controlled mass transport, and concentration of mechanical energy amidst random motion. This article explores the fundamentals of mechanically one-way materials, their potential applications across various industries, and the economic and environmental considerations related to their production and use.

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

Graphene Nanoribbons Enhancing the Electronic Conductivity and Ionic Diffusion of Graphene Electrodes for High-Performance Microsupercapacitors

The electrochemical performance of microsupercapacitors with graphene electrodes is reduced by the issue of graphene sheets aggregation,which limits electrolyte ions penetration into electrode.Increasing the space between graphene sheets in electrodes facilitates the electrolyte ions penetration,but sacrifices its electronic conductivity which also influences the charge storage ability.The challenging task is to improve the electrodes’electronic conductivity and ionic diffusion simultaneously,boosting the device’s electrochemical performance.Herein,we experimentally realize the enhancement of both electronic conductivity and ionic diffusion from 2D graphene nanoribbons assisted graphene electrode with porous layer-uponlayer structure,which is tailored by graphene nanoribbons and self-sacrificial templates ethyl cellulose.The designed electrode-based device delivers a high areal capacitance of 71 mF cm^(-2)and areal energy density of 9.83μWh cm^(-2),promising rate performance,outstanding cycling stability with 97%capacitance retention after 20000 cycles,and good mechanical properties.The strategy paves the way for fabricating high-performance graphene-based MSCs.

Band structures of strained kagome lattices

Materials with kagome lattices have attracted significant research attention due to their nontrivial features in energy bands.We theoretically investigate the evolution of electronic band structures of kagome lattices in response to uniaxial strain using both a tight-binding model and an antidot model based on a periodic muffin-tin potential.It is found that the Dirac points move with applied strain.Furthermore,the flat band of unstrained kagome lattices is found to develop into a highly anisotropic shape under a stretching strain along y direction,forming a partially flat band with a region dispersionless along ky direction while dispersive along kx direction.Our results shed light on the possibility of engineering the electronic band structures of kagome materials by mechanical strain.

Dynamic response of mountain tunnel,bridge,and embankment along the Sichuan-Tibet transportation corridor to active fault based on model tests

The Sichuan-Tibet transportation corridor is prone to numerous active faults and frequent strong earthquakes.While extensive studies have individually explored the effect of active faults and strong earthquakes on different engineering structures,their combined effect remains unclear.This research employed multiple physical model tests to investigate the dynamic response of various engineering structures,including tunnels,bridges,and embankments,under the simultaneous influence of cumulative earthquakes and stick-slip misalignment of an active fault.The prototype selected for this study was the Kanding No.2 tunnel,which crosses the Yunongxi fault zone within the Sichuan-Tibet transportation corridor.The results demonstrated that the tunnel,bridge,and embankment exhibited amplification in response to the input seismic wave,with the amplification effect gradually decreasing as the input peak ground acceleration(PGA)increased.The PGAs of different engineering structures were weakened by the fault rupture zone.Nevertheless,the misalignment of the active fault may decrease the overall stiffness of the engineering structure,leading to more severe damage,with a small contribution from seismic vibration.Additionally,the seismic vibration effect might be enlarged with the height of the engineering structure,and the tunnel is supposed to have a smaller PGA and lower dynamic earth pressure compared to bridges and embankments in strong earthquake zones crossing active faults.The findings contribute valuable insights for evaluating the dynamic response of various engineering structures crossing an active fault and provide an experimental reference for secure engineering design in the challenging conditions of the Sichuan-Tibet transportation corridor.

Analysis of Bridge-Bearing Capacity Detection and Evaluation Technology

A bridge project is taken as an example to analyze the application of bearing capacity detection and evaluation.This article provides a basic overview of the project,the application of bearing capacity detection technology,and the bearing capacity assessment analysis.It is hoped that this analysis can provide a scientific reference for the load-bearing capacity detection and evaluation work in bridge engineering projects,thereby achieving a scientific assessment of the overall load-bearing capacity of the bridge engineering structure.

Impact of Oxygen Vacancy on Band Structure Engineering of n-p Codoped Anatase TiO2

Doping with various impurities is an effective approach to improve the photoelectrochemical properties of TiO2. Here, we explore the effect of oxygen vacancy on geometric and elec- tronic properties of compensated （i.e. V-N and Cr-C） and non-compensated （i.e. V-C and Cr-N） codoped anatase TiO2 by performing extensive density functional theory calculations. Theoretical results show that oxygen vacancy prefers to the neighboring site of metal dopant （i.e. V or Cr atom）. After introduction of oxygen vacancy, the unoccupied impurity bands located within band gap of these codoped TiO2 will be filled with electrons, and the posi- tion of conduction band offset does not change obviously, which result in the reduction of photoinduced carrier recombination and the good performance for hydrogen production via water splitting. Moreover, we find that oxygen vacancy is easily introduced in V-N codoped TiO2 under O-poor condition. These theoretical insights are helpful for designing codoped TiO2 with high photoelectrochemical performance.