Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications

Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior.Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties,providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs.The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable(opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts(0–100%).Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase,band alignment/structure,carrier density,and surface reactive activity,enabling novel and promising applications.This review comprehensively elaborates on atomically substitutional engineering in TMD layers,including theoretical foundations,synthetic strategies,tailored properties,and superior applications.The emerging type of ternary TMDs,Janus TMDs,is presented specifically to highlight their typical compounds,fabrication methods,and potential applications.Finally,opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

Ductilization of Ni_3Al by Alloying with Substitutional Elements

This paper reviews recent research on ductility improvement of B-undoped Ni3Al alloys.Ni3Al binaryalloys with hypostoichiometric compositions show appreciable ductility at room temperature whenthe samples are prepared by recrystallization annealing after cold pressing,although the alloys withstoichiometric and hyperstoichiometric compositions remain brittle.Melt-spun ribbons withhypostoichiometric compositions contain fine anti-phase domains （APDs）,while no APD can beseen in melt-spun ribbons with a hyperstoichiometric composition.The ductility inhypostoichiometric Ni3Al alloys is associated with low ordering energy of the alloys.The addition ofternary elements,which have been classified as γ formers such as Pd,Pt,Cu,Co and Ag.improvesductility of Ni3Al alloys.Correspondingly,the microstructure of the melt-spun ribbons consists offine APDs.The addition of γ’ formers such as Si,Ti,Zr,V,Nb and Ta leads to brittle intergranular frac-ture.No APD was observed in the melt-spun ribbons of these ternary alloys.

Structural model of substitutional sulfur in diamond

Based on ab initio calculations,it is found that the donor center of substitutional sulfur(S)in diamond with C2v symmetry is more stable than that with C3vsymmetry,which is different from previous reports in literature.The energy difference of C2vand C3vstructures is qualitatively affected by the supercell size,and the 216-atom supercell could be proposed as the minimum to obtain stable configuration of substitutional S in diamond.Using supercells of up to 512 atoms,the donor level of substitutional S with C2vsymmetry is deep.

Determination of Substitutional Carbon in SI-GaAs Thin Wafers by Infrared Microscope

Determination of substitutional carbon in SI-GaAs thin wafers was investigated by FT-IR microscopeat room temperature for the first time.The experimental results showed that the carbon concentration inGaAs thin wafers can be measured directly with simple treatment.The calculation method of carbon concen-tration is in agreement with that for normal IR spectrum with 0.5 cm-1resolution.The resolution of1 cm-1can be taken in order to obtain a high signal-to-noise（S/N）ratio using 2.34×1016cm-2calibration factor for calculating carbon concentration at room temperature.

Antiferromagnetic ferromagnetic transition in zigzag graphene nanoribbons induced by substitutional doping

Using first-principles calculations based on density functional theory, we show that the ground state of zigzag-edged graphene nanoribbons(ZGNRs) can be transformed from antiferromagnetic(AFM) order to ferromagnetic(FM) order by changing the substitutional sites of N or B dopants. This AFM–FM transition induced by substitutional sites is found to be a consequence of the competition between the edge and bulk states. The energy sequence of the edge and bulk states near the Fermi level is reversed in the AFM and FM configurations. When the dopant is substituted near the edge of the ribbon, the extra charge from the dopant is energetically favorable to occupy the edge states in AFM configuration. When the dopant is substituted near the center, the extra charge is energetically favorable to occupy the bulk states in FM configuration. Proper substrate with weak interaction is necessary to maintain the magnetic properties of the doped ZGNRs. Our study can serve as a guide to synthesize graphene nanostructures with stable FM order for future applications to spintronic devices.

Grain-boundary segregation and grain growth in nanocrystalline substitutional solid solution alloys

A model for describing solute segregation at grain boundaries has been developed for substitutional solid solution alloys,which integrates multiple factors from atomic to microstructural scales.A concept of mo-lar Gibbs free energy of segregation was introduced to evaluate the segregating capability of the solute elements in a closed system,through which the influences of grain boundary structure,grain size,ma-terial composition,and external conditions were described.Based on the evaluation of various energy forms related to solute segregation and grain growth processes,the nature of the thermal stabilization of nanograin structures by solute segregation was disclosed.A criterion for the destabilization of nanostruc-tures,which is determined by the competition of the change rates between the molar Gibbs free energy of segregation and the total energy of grain boundaries with grain size,has been proposed.This study provided guideline to achieve high-temperature stability of nanograin structures of solid solution alloys even for the weakly segregating nanocrystalline systems.

Controllable substitutional vanadium doping in wafer-scale molybdenum disulfide films

Substitutional atomic doping of transition metal dichalcogenides(TMDs)in the chemical vapor deposition(CVD)process is a promising and effective strategy for modifying their physicochemical properties.However,the conventional CVD method only allows narrow-range modulation of the dopant concentration owing to the low reactivity of the precursors.Moreover,the growth of wafer-scale monolayer TMD films with high dopant concentrations is much more challenging.Herein,we report a facile doping approach based on liquid precursor-mediated CVD process for achieving high vanadium(V)doping in the MoS_(2)lattice with excellent doping uniformity and stability.The lateral growth of the host MoS_(2)lattice and the reactivity of the V precursor were simultaneously improved by introducing an alkali metal halide as a reaction promoter.The metal halide promoter enabled the wafer-scale synthesis of V-incorporated MoS_(2)monolayer film with excessively high doping concentrations.The excellent wafer-scale uniformity of the highly V-doped MoS_(2)film was confirmed through a series of microscopic,spectroscopic,and electrical analyses.

Synthesis of substitutional hexaboride of lanthanum and cerium La_(1-x)Ce_(x)B_(6) via aluminothermic reduction

Rare-earth hexaborides(REB_(6))are vital raw materials for cathode materials and high temperature structural ceramics that are widely applied as high-frequency electron tubes and ceramics adaptive for extreme environment,respectively.In this work,single phase substitutional solid solution REB_(6)(LaB_(6),La_(0.75)Ce_(0.25)B_(6).La_(0.5)Ce_(0.5)B_(6),La_(0.25)Ce_(0.75)B_(6) and CeB_(6))powders were prepared with the raw materials of La_(2)O_(3),CeO_(2),B_(4)C and Al powders,after calcining at 1773 K for 4 h and the following alkaline leaching.All substitutional solid solution products have homogeneous distributions of La and Ce in particles.Through microscopic morphology analysis,it is discovered that the formation of solid solution is beneficial for reducing the particle size of product,relative to LaB_(6) and CeB_(6).Moreover,Al flux plays an important role in decarbonizing reaction,and C contents of all products are below 0.4 wt%.

Off-farm employment,agriculture production activities,and household dietary diversity in environmentally and economically vulnerable areas of Asia

Access to off-farm employment has been expected to be a critical approach to ending hunger and all forms of malnutrition,two important targets of achieving Zero Hunger.This study aims to investigate the role of off-farm employment in improving dietary diversity through substitution effect and complementary effect with agricultural production activities and income effect.This study adopts Poisson/Tobit/Probit/OLS regressions and the instrument variable method based on the primary survey data collected among 1,282 households at 12 sites in environmentally and economically vulnerable areas of China,Nepal,Cambodia,Thailand,and Myanmar in 2019.The results show that off-farm employment is positively associated with household dietary diversity and the consumption of flesh meat,fish and other aquatic animals,fruits,and milk and dairy products,which are rich in protein and micronutrients.The results of mechanism analysis show that off-farm employment contributes to household dietary diversity by improving crop diversity,especially for poor households,boosting the probability of livestock raising for households with the middle one-third disposal income,and increasing household income.The positive association between off-farm employment and household dietary diversity is much higher for households with the bottom one-third disposal income,low illiteracy,and from upper-middle income countries.These findings imply that off-farm employment does play a vital role in achieving multiple benefits of poverty alleviation,malnutrition reduction,and agrobiodiversity conservation in environmentally and economically vulnerable areas.However,it may enlarge the gaps in dietary diversity between households with low human capital and from low and lower-middle income countries and those with high human capital and from middle-high countries.

Substitutional doping in 2D transition metal dichalcogenides

Two-dimensional(2D)van der Waals transition metal dichalcogenides(TMDs)are a new class of electronic materials offering tremendous opportunities for advanced technologies and fundamental studies.Similar to conventional semiconductors,substitutional doping is key to tailoring their electronic properties and enabling their device applications.Here,we review recent progress in doping methods and understanding of doping effects in group 6 TMDs(MX2,M=Mo,W;X=S,Se,Te),which are the most widely studied model 2D semiconductor system.Experimental and theoretical studies have shown that a number of different elements can substitute either M or X atoms in these materials and act as n-or p-type dopants.This review will survey the impact of substitutional doping on the electrical and optical properties of these materials,discuss open questions,and provide an outlook for further studies.

Trace element compositions of pyrite and stibnite:implications for the genesis of antimony mineralization in the Yangla Cu skarn deposit,Northwestern Yunnan,China

The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.

Manure substitution improves maize yield by promoting soil fertility and mediating the microbial community in lime concretion black soil

Synthetic nitrogen(N)fertilizer has made a great contribution to the improvement of soil fertility and productivity,but excessive application of synthetic N fertilizer may cause agroecosystem risks,such as soil acidification,groundwater contamination and biodiversity reduction.Meanwhile,organic substitution has received increasing attention for its ecologically and environmentally friendly and productivity benefits.However,the linkages between manure substitution,crop yield and the underlying microbial mechanisms remain uncertain.To bridge this gap,a three-year field experiment was conducted with five fertilization regimes:i)Control,non-fertilization;CF,conventional synthetic fertilizer application;CF_(1/2)M_(1/2),1/2 N input via synthetic fertilizer and 1/2 N input via manure;CF_(1/4)M_(3/4),1/4 N input synthetic fertilizer and 3/4 N input via manure;M,manure application.All fertilization treatments were designed to have equal N input.Our results showed that all manure substituted treatments achieved high soil fertility indexes(SFI)and productivities by increasing the soil organic carbon(SOC),total N(TN)and available phosphorus(AP)concentrations,and by altering the bacterial community diversity and composition compared with CF.SOC,AP,and the soil C:N ratio were mainly responsible for microbial community variations.The co-occurrence network revealed that SOC and AP had strong positive associations with Rhodospirillales and Burkholderiales,while TN and C:N ratio had positive and negative associations with Micromonosporaceae,respectively.These specific taxa are implicated in soil macroelement turnover.Random Forest analysis predicted that both biotic(bacterial composition and Micromonosporaceae)and abiotic(AP,SOC,SFI,and TN)factors had significant effects on crop yield.The present work strengthens our understanding of the effects of manure substitution on crop yield and provides theoretical support for optimizing fertilization strategies.

Enhancing wood efficiency through comprehensive wood flow analysis:Methodology and strategic insights

Wood,an essential natural resource in human civilization,remains widely used despite advances in technology and material substitution.The surge in greenhouse gas emissions and environmental concerns accentuates the need for optimizing wood utilization.Material flow analysis is a powerful tool for tracking material flows and stocks,aiding resource management and environmental decision-making.However,the full extent of its methodological dimensions,particularly within the context of the wood supply chain,remains relatively unexplored.In this study,we delve into the existing literature on wood flow analysis,discussing its primary objectives,materials involved,temporal and spatial scales,data sources,units,and conversion factors.Additionally,data uncertainty,data reconciliation and crucial assumptions in material flow analysis are highlighted in this paper.Key findings reveal the significance of wood cascading and substitution effects by replacing non-wood materials,where they can reduce greenhouse gas emissions more than the natural carbon sink of forests and wood products.The immediate impact of short-term wood cascading might not be as robust as the substitution effect,with energy substitution showcasing better results than material substitution.However,it's crucial to note that these conclusions could experience significant reversal from a long-term and global perspective.Strategies for improving wood efficiency involve maximizing material use,advancing construction technologies,extending product lifespans,promoting cascade use,and optimizing energy recovery processes.The study underscores the need for standardized approaches in wood flow analysis and emphasizes the potential of wood efficiency strategies in addressing environmental challenges.

Interstitial Doping of SnO_(2) Film with Li for Indium-Free Transparent Conductor

SnO_(2)films exhibit significant potential as cost-effective and high electron mobility substitutes for In_(2)O_(3)films.In this study,Li is incorporated into the interstitial site of the SnO_(2)lattice resulting in an exceptionally low resistivity of 2.028×10^(-3)Ω·cm along with a high carrier concentration of 1.398×10^(20)cm^(-3)and carrier mobility of 22.02 cm^(2)/V·s.

Atom substitution of the solid-state electrolyte Li_(10)GeP_(2)S_(12)for stabilized all-solid-state lithium metal batteries

Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical application.Among all solutions,Ge atom substitution of the solid-state electrolyte LGPS stands out as the most promising solution to this interface problem.A systematic screening framework for Ge atom substitution including ionic conductivity,thermodynamic stability,electronic and mechanical properties is utilized to solve it.For fast screening,an enhanced model Dop Net FC using chemical formulas for the dataset is adopted to predict ionic conductivity.Finally,Li_(10)SrP_(2)S_(12)(LSrPS)is screened out,which has high lithium ion conductivity(12.58 mS cm^(-1)).In addition,an enhanced migration of lithium ion across the LSr PS/Li interface is found.Meanwhile,compared to the LGPS/Li interface,LSrPS/Li interface exhibits a larger Schottky barrier(0.134 eV),smaller electron transfer region(3.103?),and enhanced ability to block additional electrons,all of which contribute to the stabilized interface.The applied theoretical atom substitution screening framework with the aid of machine learning can be extended to rapid determination of modified specific material schemes.

Associations of daily sedentary behavior,physical activity,and sleep with irritable bowel syndrome:A prospective analysis of 362,193 participants

Background:Irritable bowel syndrome(IBS)substantially affects quality of life and requires early prevention.This study aimed to elucidate the relationships between IBS and daily behaviors,including sedentary behavior(SB),physical activity(PA),and sleep.In particular,it seeks to identify healthy behaviors to reduce IBS risk,which previous studies have rarely addressed.Methods:Daily behaviors were retrieved from self-reported data of 362,193 eligible UK Biobank participants.Incident cases were determined by self-report or health care data according to RomeⅣcriteria.Results:A total of 345,388 participants were IBS-free at baseline,during a median follow-up of 8.45 years,19,885 incident IBS cases were recorded.When examined individually,SB and shorter(≤7 h/day)or longer(>7 h/day)sleep duration were each positively associated with increased IBS risk,and PA was associated with lower IBS risk.The isotemporal substitution model suggested that replacing SB with other activities could provide further protective effects against IBS risk.Among people sleeping≤7 h/day,replacing 1 h of SB with equivalent light PA,vigorous PA,or sleep was associated with 8.1%(95%confidence interval(95%CI):0.901-0.937),5.8%(95%CI:0.896-0.991),and 9.2%(95%CI:0.885-0.932)reduced IBS risk,respectively.For people sleeping>7 h/day,light and vigorous PA were associated with a 4.8%(95%CI:0.926-0.978)and a 12.0%(95%CI:0.815-0.949)lower IBS risk,respectively.These benefits were mostly independent of genetic risk for IBS.Conclusion:SB and unhealthy sleep duration are risk factors for IBS.A promising way to mitigate IBS risk for individuals sleeping≤7 h/day and for those sleeping>7 h/day appears to be by replacing SB with adequate sleep or vigorous PA,respectively,regardless of the genetic predisposition of IBS.

Reversible Mn^(2+)/Mn^(4+)double-electron redox in P3-type layer-structured sodium-ion cathode

The balance between cationic redox and oxygen redox in layer-structured cathode materials is an important issue for sodium batteries to obtain high energy density and considerable cycle stability.Oxygen redox can contribute extra capacity to increase energy density,but results in lattice instability and capacity fading caused by lattice oxygen gliding and oxygen release.In this work,reversible Mn^(2+)/Mn^(4+)redox is realized in a P3-Na_(0.65)Li_(0.2)Co_(0.05)Mn_(0.75)O_(2)cathode material with high specific capacity and structure stability via Co substitution.The contribution of oxygen redox is suppressed significantly by reversible Mn^(2+)/Mn^(4+)redox without sacrificing capacity,thus reducing lattice oxygen release and improving the structure stability.Synchrotron X-ray techniques reveal that P3 phase is well maintained in a wide voltage window of 1.5-4.5 V vs.Na^(+)/Na even at 10 C and after long-term cycling.It is disclosed that charge compensation from Co/Mn-ions contributes to the voltage region below 4.2 V and O-ions contribute to the whole voltage range.The synergistic contributions of Mn^(2+)/Mn^(4+),Co^(2+)/Co^(3+),and O^(2-)/(O_n)^(2-)redox in P3-Na_(0.65)Li_(0.2)Co_(0.05)Mn_(0.75)O_(2)lead to a high reversible capacity of 215.0 m A h g^(-1)at 0.1 C with considerable cycle stability.The strategy opens up new opportunities for the design of high capacity cathode materials for rechargeable batteries.

Yolk free egg substitute improves the serum phospholipid profile of mice with metabolic syndrome based on lipidomic analysis

In this study,the impacts of egg consumption on mice model of metabolic syndrome(Met S)were comparatively investigated.Mice were divided into five groups(n=8):normal diet group(ND),high-fat diet group(HFD),HFD with whole egg group(WE),HFD with free-yolk egg substitute group(YFES),and HFD with lovastatin group(Lov).Main biochemical indexes and a non-targeted lipidomic analysis were employed to insight the lipid profile changes in serum.It was revealed that WE could significantly improve serum biochemical indexes by reducing body weight,low-density lipoprotein cholesterol(LDL-C)and total cholesterol(TC),while increasing high-density lipoprotein cholesterol.YFES exhibited remarkably better performance in increasing phosphatidylglycerol and phosphatidic acids,while decreasing phosphatidylinositol than WE.A total of 50 differential lipids biomarkers tightly related to glycerophospholipids metabolism were screened out.Carnitine C18:2 and C12:1,SM(d18:0/12:0),and SM(d18:1/14:1)were significantly upregulated in YFES compared to WE.YFES reduced expression of SREBP-1c and Cpt1a,while did not affect the expression of PPAR-α.Sphingomyelin biomarkers were positively related to the TC(|r|>0.6),while PPAR-αwas negatively correlated with triglyceride and LDL-C levels.To sum up,YFES attenuated HFD-induced Met S by improving the serum phospholipids,which account for its modulation of glycerophospholipid metabolism.

Atomic Ni directional-substitution on ZnIn_(2)S_(4) nanosheet to achieve the equilibrium of elevated redox capacity and efficient carrier-kinetics performance in photocatalysis

It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced into the lattice of hexagonal ZnIn_(2)S_(4) nanosheets(Ni/ZnIn_(2)S_(4))via directionalsubstituting Zn atom with the facile hydrothermal method.The electronic structure calculations indicate that the introduction of Ni atom effectively extracts more electrons and acts as active site for subsequent reduction reaction.Besides the optimized light absorption range,the elevation of Efand ECBendows Ni/ZnIn_(2)S_(4) photocatalyst with the increased electron concentration and the enhanced reduction ability for surface reaction.Moreover,ultrafast transient absorption spectroscopy,as well as a series of electrochemical tests,demonstrates that Ni/ZnIn_(2)S_(4) possesses 2.15 times longer lifetime of the excited charge carriers and an order of magnitude increase for carrier mobility and separation efficiency compared with pristine ZnIn_(2)S_(4).These efficient kinetics performances of charge carriers and enhanced redox capacity synergistically boost photocatalytic activity,in which a 3-times higher conversion efficiency of nitrobenzene reduction was achieved upon Ni/ZnIn_(2)S_(4).Our study not only provides in-depth insights into the effect of atomic directional-substitution on the kinetic behavior of photogenerated charges,but also opens an avenue to the synchronous optimization of redox capacity and carrier-kinetics performance for efficient solar energy conversion.

Train post‑derailment behaviours and containment methods:a review

Railway accidents,particularly serious derailments,can lead to catastrophic consequences.Therefore,it is essential to prevent derailment escalation to reduce the likelihood of severe derailments.Train post-derailment behaviours and containment methods play a critical role in preventing derailment escalation and providing passive safety protection and accident prevention in the event of a derailment.However,despite the increasing attention on this field from academia and industry in recent years,there is a lack of systematic exploration and summarization of emerging applications and containment methods in train post-derailment research.For this reason,this paper presents a comprehensive review of existing studies on train post-derailment behaviours,encompassing various topics such as post-derailment contact-impact models,dynamic modelling and simulation techniques,and the primary factors influencing post-derailment behaviours.Significantly,this review introduces and elucidates substitute guidance mechanisms(SGMs),which serve as railway-specific passive safety protection and accident prevention measures.The various types of SGMs are depicted,and their ongoing developments and applications are explored in depth.The review additionally points out several unresolved challenges including the adverse effects of SGMs,and proposes future research directions to advance the theoretical understanding and practical application of train post-derailment behaviours and containment methods.This review seeks to be a valuable reference for railway industry professionals in preventing catastrophic derailment consequences through post-derailment containment methods.