Tuned d-band states over lanthanum doped nickel oxide for efficient oxygen evolution reaction

The d-band state of materials is an important descriptor for activity of oxygen evolution reaction(OER).For NiO materials,there is rarely concern about tuning their d-band states to tailor the OER behaviors.Herein,NiO nanocrystals with doping small amount of La^(3+)were used to regulate d-band states for promoting OER activity.Density of states calculations based on density functional theory revealed that La^(3+)doping produced upper shift of d-band center,which would induce stronger electronic interaction between surface Ni atoms and species of oxygen evolution reaction intermediates.Further density functional theory calculation illustrated that La^(3+)doped NiO possessed reduced Gibbs free energy in adsorbing species of OER intermediate.Predicted by theoretical calculations,trace La^(3+)was introduced into crystal lattice of NiO nanoparticles.The La^(3+)doped NiO nanocrystal showed much promoted OER activity than corresponding pristine NiO product.Further electrochemical analysis revealed that La^(3+)doping into NiO increased the intrinsic activity such as improved active sites and reduced charge transfer resistance.The in-situ Raman spectra suggested that NiO phase in La^(3+)doped NiO could be better maintained than pristine NiO during the OER.This work provides an effective strategy to tune the d-band center of NiO for efficient electrocatalytic OER.

Geological context and vents morphology in the ultramafic-hosted Tianxiu field, Carlsberg Ridge

The Tianxiu hydrothermal field(TXHF) located on Carlsberg Ridge is one of the few active ultramafic-hosted venting systems known in the Indian Ocean. Despite numerous investigations, there is limited understanding of its sulfide structure morphology, and the factors controlling the formation of TXHF are poorly understood. In this study, we conducted detailed seafloor mapping using visual data obtained by dives using the human-occupied vehicle(HOV) Jiaolong. The TXHF is found to be an active, off-axis, ultramafic-hosted, high-temperature hydrothermal area in which serpentine peridotite is exposed. Two main hydrothermal sites were identified, i.e., P and Y, both of which feature a complex of chimneys and beehive diffusers constituting a “chimney jungle” and isolated large steep-sided structures developed on flat-lying sulfide mounds. In addition, some sporadic inactive chimneys and outcrops of hydrothermal deposits were noted. The chimneys are rich in Fe and Zn sulfide, and lack the central fluid channel formed by focused high-temperature fluid flow. Hydrothermal venting at TXHF is likely related to low-angle detachment faults that focus and transport hydrothermal fluids away from a heat source along the valley wall. Our results complement and expand upon previous works concerning sulfide chimney morphology and their corresponding mineral paragenesis in ultramafic-hosted hydrothermal systems in the Indian Ocean and further our understanding of modern seafloor hydrothermal systems.

Engineering d-band states of(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)material for photocatalytic syngas production

The d-band states of catalytic materials participate in adsorbing reactive intermediate species and determine the catalytic behaviors in CO_(2)reduction reactions.However,surface d-band states relating to the photocatalytic CO_(2)reduction reactions behaviors are rarely concerned.Herein,a slightly amount of Cd^(2+)is decorated on the surface of(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)material(Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4))to tune the surface d-band states for improved CO_(2)+2reduction reactions.The Cd/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)is fabricated via the facile ions-exchange method to make that slightly Zn2+is substituted by Cd^(2+).The Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)exhibits much enhanced photocatalytic activity in CO_(2)reduction reactions to produce CO and water splitting to produce H_(2).Physical characterizations show that the energy band structure is not changed obviously.Density functional theory reveals that Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)possesses a closer shift of d-band center to Fermi level than(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4),suggesting easier adsorption of CO_(2)reduction reactive intermediates after Cd^(2+)decoration.Further calculations confirm that a relatively reduced adsorption Gibbs energy of reactive intermediates in CO_(2)reduction reaction is required on Zn atoms in Cd^(2+)/(CuGa)_(x)Zn_(1-2x)Ga_(2)S_(4)material,benefiting the photocatalytic CO_(2)reduction reactions.This work engineers surface d-band states by surface Cd^(2+)decoration,which gives an effective strategy to design highly efficient photocatalysts for syngas production.

Microcrystallization and lattice contraction of NiFe LDHs for enhancing water electrocatalytic oxidation

The lattice-oxygen-mediated mechanism is considered as a reasonable mechanism for the electrochemical catalytic oxygen evolution reaction(OER)of NiFe layered double hydroxides(LDHs).A NiFe LDH with distinct lattice contraction and microcrystallization was synthesized via a simple one-step method using sodium gluconate.The lattice contraction is attributed to the interaction of carbon in sodium gluconate and iron in NiFe LDH.The NiFe LDH with optimized microcrystallization and lattice contraction shows a low overpotential of 217 mV at a current density of 10 mA cm^(−2) and excellent durability of 20 h at a high current density of 100 mA cm^(−2).The results revealed that a contractive metal–oxygen bond could boost the intrinsic activity of active sites and the microcrystallization promotes an increase in the number of active sites in terms of unit area.The chemical environment of oxygen elemental characterization and resistance at different chronopotentiometry times confirm that the lattice oxygen element is indeed involved in the process of OER,supporting the lattice-oxygen-mediated mechanism of NiFe LDH.Density functional theory calculations reveal that contractive metal–oxygen bonds induced a reduction of the adsorption energy barrier of intermediate products,thus improving the intrinsic catalytic activity.The special characteristics of microcrystallization and lattice contraction of NiFe LDH provide a strategy to improve both the number and the intrinsic activity of active sites in a versatile manner.

Advanced silicon nanostructures derived from natural silicate minerals for energy storage and conversion

To effectively alleviate the ever-increasing energy crisis and environmental issues,clean and sustainable energy-related materials as well as the corresponding storage/conversion devices are in urgent demand.Silicon(Si) with the second most elemental abundance on the crust in the form of silicate or silica(SiO_(2)) minerals,is an advanced emerging material showing high performance in energy-related fields(e.g.batteries,photocatalytic hydrogen evolution).For the improved performance in industry-scale applications,Si materials with delicate nanostructures and ideal compositions in a massive production are highly cherished.On account of the reserve,low cost and diverse micro-nanostructures,silicate minerals are proposed as promising raw materials.In the article,crystal structures and the reduction approaches for silicate minerals,as well as recent progress on the as-reduced Si products for clean energy storage/conversion,are presented systematically.Moreover,some cutting-edge fields involving Si materials are discussed,which may offer deep insights into the rational design of advanced Si nanostructures for extended energy-related fields.

Engineering of carbon and other protective coating layers for stabilizing silicon anode materials

Silicon(Si)has been attracting extensive attention for rechargeable lithium(Li)‐ion batteries due to its high theoretical capacity and low potential vs Li/Li+.However,it remains challenging and problematic to stabilize the Si materials during electrochemical cycling because of the huge volume expansion,which results in losing electric contact and pulverization of Si particles.Consequently,the Si anode materials generally suffer from poor cycling,poor rate performance,and low coulomb efficiency,preventing them from practical applications.Up‐to‐date,there are numerous reports on the engineering of Si anode materials at microscale and nanoscale with significantly improved electrochemical performances.In this review,we will concentrate on various precisely designed protective layers for silicon‐based materials,including carbon layers,inorganic layers,and conductive polymer protective layer.First,we briefly introduced the alloying and failure mechanism of Si as anode materials upon electrochemical reactions.Following that,representative cases have been introduced and summarized to illustrate the purpose and advancement of protective coating layers,for instance,to alleviate pulverization and improve conductivity caused by volume expansion of Si particles during charge/discharge process,and maintain the surface stability of Si particles to form a stable solid‐electrolyte interphase layer.At last,possible strategies on the protective coating layer for stabilizing silicon anode materials that can be applied in the future have been indicated.

β-cyclodextrin as Lithium-ion Diffusion Channel with Enhanced Kinetics for Stable Silicon Anode

Silicon(Si)is regarded as a promising anode material for next-generation lithium-ion batteries due to its ultrahigh theoretical capacity.However,the drastic volume change and the continuous solid electrolyte interphase(SEI)formation during the lithiation/delithiation process seriously hinder its practical application as commercial anodes.Herein,macrocyclic betacyclodextrin(β-CD)has been designed as the diffusion channel for lithium ions at the molecular scale.The diameter of molecular channel is approximately comparable with the solvated lithium ions,which enables the transport of lithium ions and prevents the penetration of solvent molecules.Moreover,the addition ofβ-CD changes the formation behavior of SEI layer and stabilizes the Si nanoparticles.The enhanced electrochemical performances in terms of fast kinetics and improved stability have been achieved.The Si anode with the particularly selected lithium-ion diffusion channel and stabilized SEI layer exhibits a high reversible capability of 2562 m Ah g-1 after 50 cycles at the current density of 500 m A g-1,1944 m Ah g-1 after 200 cycles at the current density of 1 A g-1,and high rate performance.The novel strategy of molecular channel for lithium-ion diffusion offers new insights into the design of alloy-typed anode electrodes with high capacity for lithium-ion batteries.

Optimal set integer programming algorithm for multiple maneuvering targets tracking in clutter

The aim of this paper is to solve the problems of multitarget tracking in clutter. Firstly, the data association of measurement-to-target is formulated as an integer programming problem. Through using the linear programming （LP） based branchand-bound method and adjusting the constraint conditions, an optimal set integer programming （OSIP） algorithm is then proposed for tracking multiple non-maneuvering targets in clutter. For the case of maneuvering targets, this paper introduces the OSIP algorithm into the filtering step of the interacting multiple model （IMM） algorithm resulting in the IMM based on OSIP algorithm. Extensive Monte Carlo simulations show that the presented algorithms can obtain superior estimations even in the case of high density noises.

Anchoring Active Sites by Pt_(2)FeNi Alloy Nanoparticles on NiFe Layered Double Hydroxides for Efficient Electrocatalytic Oxygen Evolution Reaction

Strategy of anchoring alloy nanoparticles made up of the efficient catalytic element(e.g.,Ni,Fe)on dodecyl sulfate(DS^(-))-intercalated NiFe layered double hydroxides(DS^(-)-NiFe LDH)obtained by a convenient one-step hydrothermal coprecipitation method for essentially enhancing oxygen evolution reaction(OER)performance was proposed.The results of structural characterization indicate Pt_(2)FeNi alloy nanoparticles evenly distribute on the surface of DS^(-)-NiFe LDH.The sizes of the Pt_(2)FeNi nanoparticles,closely related to their OER performance,could be wellcontrolled by adjusting the amount of H;PtCl;addition.The composite structure of as-prepared product was stable during processes of synthesis,exfoliation,self-assembly,and subsequent electrocatalytic OER.Rigorous electrochemical test proving the contributing catalytic active sites was located at the interface between Pt_(2)FeNi and DS^(-)-NiFe LDH,and the Ni and Fe were the major active elements while O atoms are adsorption sites.The formation of Pt_(2)FeNi nanoparticles could greatly prompt the reduction of Tafel slope.The best-performing Pt_(2)FeNi/DS^(-)-NiFe LDH with a Pt content of 0.98 wt%achieved low overpotential of 204 mV at 10 mA cm^(-2)and 262 mV at 50 mA cm^(-2).This work provides a convenient and effective strategy to create additional active sites for enhancing OER performance of NiFe LDH and make contribution to its wide application.

三功能共晶溶剂添加剂用于高性能锂金属电池

Rational carbonate electrolyte chemistry is critical for the development of high-voltage lithium metal batteries(LMBs).However,the implementation of traditional carbonate electrolyte is greatly hindered by the generation of an unstable electrode interphase and corrosive by-product(HF).Herein,we propose a triple-function eutectic solvent additive of N-methylacetamide(NmAc)with LiNO_(3) to enhance the stability and compatibility of carbonate electrolyte.Firstly,the addition of NmAc significantly improves the solubility of LiNO_(3) in carbonate electrolyte by forming an eutectic pair,which regulates the Li~+solvation structure and leads to dense and homogenous Li plating.Secondly,the hydrolysis of acidic PF_5 is effectively alleviated due to the strong complexation of NmAc with PF_5,thus reducing the generation of corrosive HF.In addition,the optimized cathode electrolyte interphase layer decreases the structural degradation and transition metal dissolution.Consequently,Li||LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)cells with the designed electrolyte deliver superior long-term cycle reversibility and excellent rate capability.This study unveils the rationale for incorporating eutectic solvent additives within carbonate electrolytes,which significantly contribute to the advancement of their practical application for high-voltage LMBs.

Honeycomb-like biochar framework coupled with Fe_(3)O_(4)/FeS nanoparticles as efficient heterogeneous Fenton catalyst for phenol degradation

Achieving an efficient and stable heterogeneous Fenton reaction over a wide pH range is of great significance for wastewater treatment.Here,a pollen-derived biochar catalyst with a unique honeycomb-like structure,coupled with the dispersion of magnetic Fe_(3)O_(4)/FeS(Fe/S)nanoparticles,was synthesized by simple impregnation precursor,followed by pyrolysis.The prepared Fe/S-biochar catalyst demonstrated outstanding phenol degradation efficiency across a wide pH range,with 98%of which eliminated even under neutral conditions(pH 7.0).The high catalytic activity was due to the multilevel porous structure of pollenderived biochar provided enough active sites and allowed for better electron transfer,then increases oxidation ability to promote the reaction.Moreover,the acid microenvironment formed by SO_(4)^(2-)group from Fe/S composite extended the pH range for Fenton reaction,and S^(2-)facilitated the conversion of≡Fe^(3+)to≡Fe^(2+),resulting in remarkable degradation efficiency.Further,biochar can effectively promote cycling stability by limiting Fe leaching.This work may provide a general strategy for designing 3D framework biochar-based Fe/S catalysts with excellent performance for heterogeneous Fenton reactions.

Recent advances in multifunctional metal-organic frameworks for lithium metal batteries

In view of novel materials in the field of lithium metal batteries(LMBs), metal-organic frameworks(MOFs) have attracted extensive research interest owing to their controllable pore size, unsaturated metal sites and multifunctional organic groups. A variety of MOFs have been elaborately calculated and synthesized to be applied as separator coating, electrolyte modulators and solid-state electrolyte fillers in LMBs. In this mini-review, we summarize the mechanism of MOFs to limit the migration of anions, improve the Li-ion transference number and prolong the lifespan of LMBs. Suitable pore structure of MOFs can physically restrict the movement of Li^(+). Unsaturated metal sites can adsorb anions by electrostatic interaction. In addition,multifunctional organic functional groups that limit the migration of anions are discussed. Finally, the key challenges and perspectives in the development direction of MOFs-based separators and electrolytes are further elaborated.

Boosting charge transfer via interface charge reconstruction between amorphous NiFe-LDH and crystalline NiCo_(2)O_(4)for efficient alkaline water/seawater oxidation

Electrocatalysts with optimal efficiency and durability for the oxygen evolution reaction(OER)are becoming increasingly important as the demand for alkaline water/seawater electrolysis technology grows.Herein,a novel rose-shaped NiFe-layered double hydroxide(LDH)/NiCo_(2)O_(4)composed of amorphous wrinkled NiFe-LDH and highly crystalline NiCo_(2)O_(4)was synthesized with rich heterointerfaces.Many unsaturated metal sites are generated due to significant charge reconstruction at the heterointerface between the crystalline and amorphous phases.These metal sites could trigger and provide more active sites.The density functional theory(DFT)reveals that a new charge transfer channel(Co-Fe)was formed at the heterointerface between NiFe-LDH as electron acceptor and NiCo_(2)O_(4)as electron donor.The new charge transfer channel boosts interfacial charge transfer and enhances catalytic efficiency.The NiFe-LDH/NiCo_(2)O_(4)/nickel foam(NF)drives current densities of 10 and 100 mA·cm−2 with overpotentials of 193 and 236 mV,respectively.The composite electrode demonstrates a fast turnover frequency(0.0143 s−1)at 1.45 V vs.RHE(RHE=reversible hydrogen electrode),which is 5.5 times greater than pure NiCo_(2)O_(4),suggesting its superior intrinsic activity.Additionally,NiFe-LDH/NiCo_(2)O_(4)/NF electrode exhibited negligible degradation after 150 h of uninterrupted running in alkaline seawater oxidation.This study introduces a method for preparing high-efficiency electrocatalysts utilized in alkaline water/seawater electrolysis.

Sulfide metallogenic model for the ultraslow-spreading Southwest Indian Ridge

Polymetallic sulfides present in mid-ocean ridges(MORs)have become important strategic resources for humans,and a scientific metallogenic model is necessary for the investigation and exploration of these resources.Compared to fast-and slow-spreading MORs,ultraslow-spreading MORs show substantial differences in magma supply,tectonic activity,and oceanic crust structures.However,information on hydrothermal circulation and a metallogenic model related to sulfides along the ultraslow-spreading ridges is still limited,which hinders further exploration of these resources.In this study,the distribution of hydrothermal activities,as well as the characteristics of the structures,heat sources,fluid pathways,host rock types,fluid properties,and sulfide assemblages in typical hydrothermal fields along the ultraslow-spreading Southwest Indian Ridge(SWIR),have been studied.It is concluded that the hydrothermal systems along the SWIR can be categorized into three types,including local enhanced magma-controlled,one-way detachment/high-angle large-offset fault-controlled,and flip-flop detachment-controlled types,which are further categorized into five subtypes based on their distinct geological backgrounds.Herein,we present a sulfide metallogenic model called Local Enhanced Heat Supply-Deep Faults(eHeat-dFault)for the SWIR.The overall spreading rate remains almost constant(14-18 mm/year),while the magma supply is heterogeneous in the segment scale along the SWIR.Over the past two decades,various hydrothermal systems and sulfide deposits have been identified along the SWIR.A deep magma chamber(4-9 km)is developed in the ridge segment with sufficient magma supply owing to the local enhanced magma supply,while long-lived active deep detachment faults(up to 13 km)with associated metallogenic belts are developed in ridge segments with poor magma supply.Hence,the ultraslow-spreading MORs fulfill the necessary conditions of a sustained heat source and stable hydrothermal pathway for the formation of large-scale polymetallic sulfide deposits.The number of hydrothermal fields detected in the investigation area is 2-3 times that predicted by the traditional Spreading Rate-Magma Flux model,demonstrating its significant endowment for sulfide resources.A balance between magma supply and faulting may influence the type and depth of hydrothermal circulation,the frequency of hydrothermal activity along the axis,and the scale of sulfide deposits.Spreading rate was previously believed to control heat sources,magma supply,and tectonic processes.However,for the SWIR,we suggest that local enhanced heat supply and deep detachment faults have a greater influence than the spreading rate on hydrothermal circulation and sulfide mineralization.The eHeat-dFault sulfide metallogenic model proposed herein could provide guidance for further exploration and research on polymetallic sulfides in ultraslow-spreading SWIR.

Functional characterization of sensory neuron membrane protein 1a involved in sex pheromone detection of Apolygus lucorum(Hemiptera:Miridae)

The mirid bug Apolygus lucorum(Hemiptera:Miridae)is a polyphagous pest that affects a wide range of host plants.Its control remains challenging mainly due to its rapid reproduction,necessitating an understanding of sex pheromone communication.The recognition of sex pheromones is vital for courtship and mating behaviors,and is mediated by various chemosensory-associated proteins.Among these,sensory neuron membrane protein(SNMP),a CD36-related protein,is suggested to play crucial roles in detecting sex pheromones.In this study,we employed transcriptomic and genomic data from A.lucorum and phylogenetic approaches,and identified four putative SNMP genes(AlucSNMP1a,AlucSNMP1b,AlucSNMP2a,and AlucSNMP2b)with full open reading frames.Expression analysis revealed the ubiquitous presence of AlucSNMP transcripts in multiple tissues,with only AlucSNMP1a exhibiting male-biased expression in the antennae,suggesting its potential role in male chemosensation.Functional analysis using the Xenopus oocyte expression system,coupled with two-electrode voltage clamp recording,demonstrated that the co-expression of AlucSNMP1a with specific pheromone receptors(PRs)and the Odorant receptor co-receptor(Orco)significantly enhanced electrophysiological responses to sex pheromones compared to the co-expression of PRs and Orco alone.Moreover,the results indicated that the presence of AlucSNMP1a not only affected the responsiveness to sex pheromones but also influenced the kinetics(activation and inactivation)of the induced signals.In contrast,the co-expression of AlucSNMP1b with AlucPR/Orco complexes had no impact on the inward currents induced by two pheromone compounds.An examination of the selective pressures on SNMP1 genes across 20 species indicated strong purifying selection,implying potential functional conservation in various insects.These findings highlight the crucial role of AlucSNMP1a in the response to sex pheromones.

Hollow spherical rare-earth-doped yttrium oxysulfate： A novel structure for upconversion

A facile biomolecule-assisted hydrothermal route followed by calcination has been employed for the preparation of monoclinic yttrium oxysulfate hollow spheres doped with other rare-earth ions （Yb3＋ and Eu3＋ or Er3＋）. The formation of hollow spheres may involve Ostwald ripening. The resulting hybrid materials were used for upconversion applications. The host crystal structure allows the easy co-doping of two different rare-earth metal ions without significantly changing the host lattice. The luminescent properties were affected by the ratio and concentration of dopant rare-earth metal ions due to energy transfer and the symmetry of the crystal field. The type of luminescent center and the crystallinity of samples were also shown to have a significant influence on the optical properties of the as-prepared products.

Optimized weak measurement of orbital angular momentum-induced beam shifts in optical reflection

Tiny but universal beam shifts occur when a polarized light beam is reflected upon a planar interface.Although the beam shifts of Gaussian beams have been measured by the weak measurement technique, the weak measurement for orbital angular momentum(OAM)-induced spatial shifts of vortex beams is still missing.Here, by elaborately choosing the preselection and postselection states, the tiny OAM-induced Goos–H?nchen and Imbert–Fedorov shifts are amplified at an air–prism interface. The maximum shifts along directions both parallel and perpendicular to the incident plane are theoretically predicted and experimentally verified with optimal preselection and postselection states. These maximum shifts can be used to determine the OAM of vortex beams.

3D multicore-shell CoSn nanoboxes encapsulated in porous carbon as anode for lithium-ion batteries

Due to its high theoretical capacity and appropriate potential platform,tin-based alloy materials are expected to be a competitive candidate for the next-generation high performance anodes of lithium-ion batteries.Nevertheless,the immense volume change during the lithium-ion insert process leads to severe disadvantages of structural damage and capacity fade,which limits its practical application.In this work,a three-dimensional(3 D)multicore-shell hollow nanobox encapsulated by carbon layer is obtained via a three-step method of hydrothermal reaction,annealing and alkali etching.During the electrochemical reactions,the CoSn@void@C nanoboxes provide internal space to compensate the volumetric change upon the lithiation of Sn,while the inactive component of Co acts as chemical buffers to withstand the anisotropic expansion of nanoparticles.Owing to the above-mentioned advantages,the elaborated anode delivers an excellent capacity of 788.2 m Ah/g at 100 m A/g after 100 cycles and considerable capacity retention of 519.2 mAh/g even at a high current density of 1 A/g after 300 cycles.The superior stability and high performance indicate its capability as promising anodes for lithium-ion batteries.