Pulsed laser interference patterning of transition-metal carbides for stable alkaline water electrolysis kinetics

We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.

Recent advances of transition-metal metaphosphates for efficient electrocatalytic water splitting

Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a high content of P(which exists as PO3-),and therefore have been recognized as highly efficient catalysts for oxygen evolution reaction(OER)and the bottleneck of electrochemical water splitting.Furthermore,TMMPs can also contribute to hydrogen evolution reaction(HER)in alkaline and neutral media by facilitating water dissociation,and thus,overall water splitting can be achieved using this kind of material.In this timely review,we summarize the recent advances in the synthesis of TMMPs and their applications in OER and HER.We present a brief introduction of the structure and synthetic strategies of TMMPs in the first two parts.Then,we review the latest progress made in research on TMMPs as OER,HER,and overall water-splitting electrocatalysts.In this part,the intrinsic activity of TMMPs as well as the current strategy for improving the catalytic activity will be discussed systematically.Finally,we present the future opportunities and the remaining challenges for the application of TMMPs in the electrocatalysis field.

Effect of coenzyme Q10 supplementation on post-vitrification mouse embryo development

Objective:To investigate the effects of coenzyme Q10(CoQ10)supplementation on post-vitrification embryo development and gross morphology.Methods:Balb/c mouse embryos were cultured in potassium simplex optimised medium(KSOM)with varying CoQ10 concentrations[0(control),20,40,and 60μM].The most effective CoQ10 concentration(40μM)was selected for subsequent post-vitrification morphology study.Embryos were randomly divided into four groups:Group A(non-vitrified without CoQ10),Group B(non-vitrified with CoQ10),Group C(vitrified without CoQ10),and Group D(vitrified with CoQ10),followed by vitrification at the 8-cell stage.Survival rates and development until the blastocyst stage were evaluated through morphological examinations using ASEBIR's system,distinguishing normal and abnormal embryos.Results:Supplementation of 40μM CoQ10 significantly increased blastocyst formation(95%)compared to the control group(92%),20μM(62%),and 60μM(56%)(P<0.001).Following vitrification,Group D exhibited a significant increase in blastocyst formation(92%)compared to Group C(82%)(P<0.05).Morphological assessments indicated superior embryo quality in Group B over Group D during the cleavage stage,morula,and blastocyst(P<0.05).Conclusions:CoQ10 supplementation exhibits promising potential to enhance preimplantation embryo development,increase blastocyst formation rates,and improve embryo quality post-vitrification.This offers a promising approach to mitigate oxidative stress on embryos,potentially improving overall assisted reproductive technology outcomes.

Dioxygen Affinities and Catalytic Epoxidation Performanceof Transition-Metal Hydroxamates

The dioxygen affinities and catalytic epoxidation performance of transition-metal hydroxamates were investigated for the first time. The effects of substituents on these properties were also discussed in the paper.

Layered transition-metal hydroxides for alkaline hydrogen evolution reaction

Hydrogen is a promising sustainable energy to replace fossil fuels owning to its high specific energy and environmental friendliness.Alkaline water electrolysis has been considered as one of the most prospective technologies for large scale hydrogen production.To boost the sluggish kinetics of hydrogen evolution reaction(HER)in alkaline media,abundant materials have been designed and fabricated.Herein,we summarize the key achievements in the development of layered transition-metal hydroxides[TM(OH)x]for efficient alkaline HER.Based on the structure of TM(OH)x,the mechanism of synergistic effect between TM(OH)x and HER active materials is illuminated firstly.Then,recent progress of TM(OH)x-based HER catalysts to optimize the synergistic effect are categorized as TM(OH)x and active materials,including species,structure,morphology and interaction relationship.Furthermore,TM(OH)x-based overall water splitting electrocatalysts and electrodes are summarized in the design principles for high activity and stability.Finally,some of key challenges for further developments and applications of hydrogen production are proposed.

Exploring single atom catalysts of transition-metal doped phosphorus carbide monolayer for HER:A first-principles study

Hydrogen has been identified as one of the most promising sustainable and clean energy. Developing hydrogen evolution reaction(HER) catalyst with high activity is essential for satisfying the future requirements. Considering novel advantages of two-dimensional materials and high catalytic activity of atomic transition metal, in this study, using density functional theory calculation, the HER on single transitionmetal(23 different TM atoms) doped phosphorus carbide monolayer(α-PC) has been investigated. The Volmer–Tafel and Volmer–Heyrovsky reaction mechanisms, and the stability of the most promising HER catalyst are also included. The results show that Ir-αPC with high physical and thermal stability has the most optimal value of Gibbs free adsorption energy for H atom. The relationship of d band center and the HER activity shows a volcano-like curve. The calculation of reaction energy barrier indicates that the Volmer-Heyrovsky step is more favorable than the Volmer-Tafel step.

Environmental Analysis with 2D Transition-Metal Dichalcogenide-Based Field-Effect Transistors

Field-effect transistors(FETs)present highly sensitive,rapid,and in situ detection capability in chemical and biological analysis.Recently,two-dimensional(2D)transition-metal dichalcogenides(TMDCs)attract significant attention as FET channel due to their unique structures and outstanding properties.With the booming of studies on TMDC FETs,we aim to give a timely review on TMDCbased FET sensors for environmental analysis in different media.First,theoretical basics on TMDC and FET sensor are introduced.Then,recent advances of TMDC FET sensor for pollutant detection in gaseous and aqueous media are,respectively,discussed.At last,future perspectives and challenges in practical application and commercialization are given for TMDC FET sensors.This article provides an overview on TMDC sensors for a wide variety of analytes with an emphasize on the increasing demand of advanced sensing technologies in environmental analysis.

Role of transition-metal electrocatalysts for oxygen evolution with Si-based photoanodes

A comprehensive understanding of the role of the electrocatalyst in photoelectrochemical(PEC)water splitting is central to improving its performance.Herein,taking the Si-based photoanodes(n^(+)p-Si/SiO_(x)/Fe/FeOx/MOOH,M=Fe,Co,Ni)as a model system,we investigate the effect of the transition-metal electrocatalysts on the oxygen evolution reaction(OER).Among the photoanodes with the three different electrocatalysts,the best OER activity,with a low-onset potential of∼1.01 VRHE,a high photocurrent density of 24.10 mA cm^(-2)at 1.23 VRHE,and a remarkable saturation photocurrent density of 38.82 mA cm^(-2),was obtained with the NiOOH overlayer under AM 1.5G simulated sunlight(100 mW cm^(-2))in 1 M KOH electrolyte.The optimal interfacial engineering for electrocatalysts plays a key role for achieving high performance because it promotes interfacial charge transport,provides a larger number of surface active sites,and results in higher OER activity,compared to other electrocatalysts.This study provides insights into how electrocatalysts function in water-splitting devices to guide future studies of solar energy conversion.

Electronic structure and magnetic properties of substitutional transition-metal atoms in GaN nanotubes

The electronic structure and magnetic properties of the transition-metal （TM） atoms （Sc-Zn, Pt and Au） doped zigzag GaN single-walled nanotubes （NTs） are investigated using first-principles spin-polarized density functional calculations. Our results show that the bindings of all TM atoms are stable with the binding energy in the range of 6-16 eV. The Sc- and V-doped GaN NTs exhibit a nonmagnetic behavior. The GaN NTs doped with Ti, Mn, Ni, Cu and Pt are antiferromagnetic. On the contrary, the Cr-, Fe-, Co-, Zn- and Au-doped GaN NTs show the ferromagnetic characteristics. The Mn- and Co- doped GaN NTs induce the largest local moment of 4#B among these TM atoms. The local magnetic moment is dominated by the contribution from the substitutional TM atom and the N atoms bonded with it.

NMR and NQR studies on transition-metal arsenide superconductors LaRu2As2,KCa2Fe4As4F2,and A2Cr3As3

We report 75As-nuclear magnetic resonance(NMR)and nuclear quadrupole resonance(NQR)measurements on transition-metal arsenides LaRu2As2,KCa2Fe4As4F2,and A2Cr3As3.In the superconducting state of LaRu2As2,a Hebel–Slichter coherence peak is found in the temperature dependence of the spin-lattice relaxation rate 1/T1 just below Tc,which indicates that LaRu2As2 is a full-gap superperconducor.For KCa2Fe4As4F2,antiferromagnetic spin fluctuations are observed in the normal state.We further find that the anisotropy rate RAF=Tc 1/Tab 1 is small and temperature independent,implying that the low energy spin fluctuations are isotropic in spin space.Our results indicate that KCa2Fe4As4F2 is a moderately overdoped iron-arsenide high-temperature superconductor with a stoichiometric composition.For A2Cr3As3(A=Na,K,Rb,Cs),we calculate the electric field gradient by first-principle method and assign the 75As-NQR peaks to two crystallographically different As sites,paving the way for further NMR investigation.

Dioxygen Affinities and Biomimetic Catalytic Performance of Transition-metal Complexes with Benzoin Schiff Bases

The oxygenation constants of transition-metal complexes with benzoin Schiff bases were measured and these complexes were first employed as models for mimicking monooxygenase in catalytic epoxidation of styrene. The highest conversion and selectivity were up to 39.6% and 100% respectively at ambient temperature and pressure. The effects of structures of the bridge group R in the ligands on the dioxygen affinities and catalytic activities to epoxidize styrene were also investigated.

Interfacial engineering of transition-metal sulfides heterostructures with built-in electric-field effects for enhanced oxygen evolution reaction

Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transition-metal electrocatalysts still suffer from low activity and durability on account of poor interfacial reaction kinetics.In this work,a facile solid-state synthesis strategy is developed to construct transition-metal sulfides heterostructures(denoted as MS_(2)/NiS_(2),M=Mo or W)for boosting OER electrocatalysis.As a result,MoS2/NiS2 and WS2/NiS2 show lower overpotentials of 300 mV and 320 mV to achieve the current density of 10 mA·cm^(-2),and smaller Tafel slopes of 60 mV.dec^(-1) and 83 mV.dec^(-1)in 1 mol·L^(-1) KOH,respectively,in comparison with the single MoS2,WS2,NiS2,as well as even the benchmark RuO2.The experiments reveal that the designed heterostructures have strong electronic interactions and spontaneously develop a built-in electric field at the heterointerface with uneven charge distribution based on the difference of band structures,which promote interfacial charge transfer,improve absorptivity of OH-,and modulate the energy level more comparable to the OER.Thus,the designed transition-metal sulfides heterostructures exhibit a remarkably high electrocatalytic activity for OER.This study provides a simple strategy to manipulate the heterostructure interface via an energy level engineering method for OER and can be extended to fabricate other heterostructures for various energy-related applications.

Dioxygen Affinities and Biomimetic Catalytic Performance of Transition-metal Complexes with Crowned Bis-Schiff Bases

The dioxygen affinities and biomimetic catalytic performance of transition-metal complexes with (15-crown-5) salophen and its substituted derivatives Mere examined. The oxygenation constants of Co(II) complexes with crowned bis-Schiff bases were measured and their Mn(III) complexes were employed as models to mimic monooxygenase in catalytic epoxidation of styrene. The highest conversion and selectivity were up to 57.2% and 100% respectively at ambient temperature and pressure. The effects of crown ether ring and substituents R on the dioxygen affinities and catalytic activities were also investigated through comparing with the uncrowned analogues.

Structural and electronic properties of transition-metal chalcogenides Mo5S4 nanowires

Transition-metal chalcogenide nanowires(TMCN) as a viable candidate for nanoscale applications have been attracting much attention for the last few decades. Starting from the rigid building block of M6 octahedra(M = transition metal),depending on the way of connection between M6 and decoration by chalcogenide atoms, multiple types of extended TMCN nanowires can be constructed based on some basic rules of backbone construction proposed here. Note that the well-known Chevrel-phase based M6X6 and M6X9(X = chalcogenide atom) nanowires, which are among our proposed structures, have been successfully synthesized by experiment and well studied. More interestingly, based on the construction principles, we predict three new structural phases(the cap, edge, and C&E phases) of Mo5S4, one of which(the edge phase) has been obtained by top-down electron beam lithography on two-dimensional MoS2, and the C&E phase is yet to be synthesized but appears more stable than the edge phase. The stability of the new phases of Mo5S4 is further substantiated by crystal orbital overlapping population(COOP), phonon dispersion relation, and thermodynamic calculation. The barrier of the structural transition between different phases of Mo5S4 shows that it is very likely to realize an conversion from the experimentally achieved structure to the most stable C&E phase. The calculated electronic structure shows an interesting band nesting between valence and conduction bands of the C&E Mo5S4 phase, suggesting that such a nanowire structure can be well suitable for optoelectronic sensor applications.

Microstructured hydroxyl environments and Raman spectroscopy in selected basic transition-metal halides

Raman vibrational spectra of the selected basic （hydroxyl OH and deuteroxyl OD） transition-metal halides, geomet- rically frustrated material series α-, β-, γ-Cu2（OH）3Cl, α-Cu2（OH）3Br, β-Ni2（OH）3Cl, β-Co2（OH）3Cl, β-Co2（OH）3Br, γ-Cu2（OD）3Cl, and β-Co2（OD）3Cl are measured at room temperature and analysed to investigate the relationship be- tween the microstructured OH environments and their respective Raman spectra. Among these selected samples, the last two are used to determine the OH stretching vibration region （3600 cm-1-3300 cm-1） and OH bending vibra- tion region （1000 cm-1-600 cm-1） of OH systems in the spectra. Through the comparative analysis of the distances d（metal-O）, d（O-halogen）, and d（OH）, the strong metal-O interaction and trimeric hydrogen bond （Car, C8 or C1 symmetry） are found in every material, but both determine simultaneously an ultimate d（OH）, and therefore an OH stretching vibration frequency. According to the approximately linear relationship between the OH stretching vibration frequency and d（OH）, some unavailable d（OH） are guessed and some doubtful d（OH） are suggested to be corrected. In addition, it is demonstrated in brief that the OH bending vibration frequency is also of importance to check the more detailed crystal microstructure relating to the OH group.

Topological Transition in Monolayer Blue Phosphorene with Transition-Metal Adatom under Strain

We carried out first-principles calculations to investigate the electronic properties of the monolayer blue phosphorene(BlueP)decorated by the group-IVB transition-metal adatoms(Cr,Mo and W),and found that the Cr-decorated BlueP is a magnetic half metal,while the Mo-and W-decorated BlueP are semiconductors with band gaps smaller than 0.2 eV.Compressive biaxial strains make the band gaps close and reopen,and band inversions occur during this process,which induces topological transitions in the Mo-decorated BlueP(with strain of-5.75%)and W-decorated BlueP(with strain of-4.25%)from normal insulators to topological insulators(TIs).The TI gap is 94 meV for the Mo-decorated BlueP and218 me V for the W-decorated BlueP.Such large TI gaps demonstrate the possibility to engineer topological phases in the monolayer BlueP with transition-metal adatoms at high temperature.

Dioxygen Affinities and Biomimetic Catalytic Oxidation Performance of Transition-metal Complexes with Unsymmetrical Bis-Schiff Bases

The oxygenation constants and thermodynamic parameter (ΔHo, ΔSo) of Co (II) complexes with unsymmetrical bis-Schiff baeses were measured and their Mn(III) complexes as models of mimicking monooxygenase were employed to catalyze epoxidation of styrene. The effect of substituent R in a salicylidene of ML1~ML4 [ M = Co (II), Mn (III)Cl ] on the dioxygen affinities and biomimetic catalytic oxidation performance were also investigated. Among them, the MnL4Cl containing a pendant benzoaza crown ether ring showed highest conversion and selectiviy up to 54.9% and 96.9% respectively.

Discovery of Two-Dimensional Quantum Spin Hall Effect in Triangular Transition-Metal Carbides

Though the quantum spin Hall effect（QSHE） in two-dimensional（2 D） crystals has been widely explored, the experimental realization of quantum transport properties is only limited to HgTe/CdTe or InAs/GaSb quantum wells. Here we employ a tight-binding model on the basis of d（z^2）, d（xy）, and d（x^2-y^2） orbitals to propose QSHE in the triangular lattice, which are driven by a crossing of electronic bands at the Γ point. Remarkably, 2 D oxidized Mxenes W2 M2 C3 are ideal materials with nontrivial gap of 0.12 eV, facilitating room-temperature observations in experiments. We also find that the nontrivially topological properties of these materials are sensitive to the cooperative effect of the electron correlation and spin-orbit coupling. Due to the feasible exfoliation from its 3 D MAX phase, our work paves a new direction towards realizing QSHE with low dissipation.

Structural,electronic,and magnetic properties of transition-metal atom adsorbed two-dimensional GaAs nanosheet

By using first-principles calculations within the framework of density functional theory,the electronic and magnetic properties of 3d transitional metal（TM） atoms（from Sc to Zn） adsorbed monolayer Ga As nanosheets（Ga As NSs） are systematically investigated.Upon TM atom adsorption,Ga As NS,which is a nonmagnetic semiconductor,can be tuned into a magnetic semiconductor（Sc,V,and Fe adsorption）,a half-metal（Mn adsorption）,or a metal（Co and Cu adsorption）.Our calculations show that the strong p–d hybridization between the 3d orbit of TM atoms and the 4p orbit of neighboring As atoms is responsible for the formation of chemical bonds and the origin of magnetism in the Ga As NSs with Sc,V,and Fe adsorption.However,the Mn 3d orbit with more unpaired electrons hybridizes not only with the As 4p orbit but also with the Ga 4p orbit,resulting in a stronger exchange interaction.Our results may be useful for electronic and magnetic applications of Ga As NS-based materials.

Effects of dietary coenzyme Q10 supplementation during gestation on the embryonic survival and reproductive performance of high‑parity sows

Background Fertility declines in high-parity sows.This study investigated whether parity-dependent declines in embryonic survival and reproductive performance could be restored by dietary coenzyme Q10(CoQ10)supplementation.Methods Two experiments were performed.In Exp.1,30 young sows that had completed their 2nd parity and 30 high-parity sows that had completed their 10^(th)parity,were fed either a control diet(CON)or a CON diet supple-mented with 1 g/kg CoQ10(+CoQ10)from mating until slaughter at day 28 of gestation.In Exp.2,a total of 314 post-weaning sows with two to nine parities were fed the CON or+CoQ10 diets from mating throughout gestation.Results In Exp.1,both young and high-parity sows had a similar number of corpora lutea,but high-parity sows had lower plasma CoQ10 concentrations,down-regulated genes involved with de novo CoQ10 synthesis in the endome-trium tissues,and greater levels of oxidative stress markers in plasma and endometrium tissues.High-parity sows had fewer total embryos and alive embryos,lower embryonic survival,and greater embryo mortality than young sows.Dietary CoQ10 supplementation increased the number of live embryos and the embryonic survival rate to levels simi-lar to those of young sows,as well as lowering the levels of oxidative stress markers.In Exp.2,sows showed a parity-dependent decline in plasma CoQ10 levels,and sows with more than four parities showed a progressive decline in the number of total births,live births,and piglets born effective.Dietary supplementation with CoQ10 increased the number of total births,live births,and born effective,and decreased the intra-litter covariation coefficients and the percentage of sows requiring farrowing assistance during parturition.Conclusions Dietary CoQ10 supplementation can improve the embryonic survival and reproductive performance of gestating sows with high parity,probably by improving the development of uterine function.