Electronic structure and ultraviolet spectra of p-C_(6)H_(4)-C_(20)

Geometry optimization of p-C_(6)H_(4)-connected cyclo[20]carbon(p-C_(6)H_(4)-C_(20))was carried out at M062X/6-311G(d,p)level,three kinds of bond orders(Mayer,Laplacian,and Wiberg),electron-hole distributions,localized orbital locators(LOL),and infrared(IR)spectrum were also performed at the same level.Based on TD-DFT M062X/6-311G(d,p)method,the first 20 excited states and ultraviolet(UV)spectra of p-C_(6)H_(4)-C_(20) were calculated.Calculation results of π-electron delocalization analyses prove thatπ-electron delocalization of p-C_(6)H_(4)-C_(20) is more likely to occur on shorter C-C bonds rather than longer C-C bonds,and inside/outside of the ring plane rather than above/below the ring plane.Two absorption peaks of p-C_(6)H_(4)-C_(20) locate at about 319 nm and 236 nm,respectively.

Molecular simulation study of the microstructures and properties of pyridinium ionic liquid[HPy][BF_(4)]mixed with acetonitrile

The microstructures and thermodynamic properties of mixed systems comprising pyridinium ionic liquid[HPy][BF_(4)]and acetonitrile at different mole fractions were studied using molecular dynamics simulation in this work.The following properties were determined:density,self-diffusion coefficient,excess molar volume,and radial distribution function.The results show that with an increase in the mole fraction of[HPy][BF_(4)],the self-diffusion coefficient decreases.Additionally,the excess molar volume initially decreases,reaches a minimum,and then increases.The rules of radial distribution functions(RDFs)of characteristic atoms are different.With increasing the mole fraction of[HPy][BF_(4)],the first peak of the RDFs of HA1-F decreases,while that of CT6-CT6 rises at first and then decreases.This indicates that the solvent molecules affect the polar and non-polar regions of[HPy][BF_(4)]differently.

Deep Learning Hybrid Model for Lithium-Ion Battery Aging Estimation and Prediction

The degradation process of lithium-ion batteries is intricately linked to their entire lifecycle as power sources and energy storage devices,encompassing aspects such as performance delivery and cycling utilization.Consequently,the accurate and expedient estimation or prediction of the aging state of lithium-ion batteries has garnered extensive attention.Nonetheless,prevailing research predominantly concentrates on either aging estimation or prediction,neglecting the dynamic fusion of both facets.This paper proposes a hybrid model for capacity aging estimation and prediction based on deep learning,wherein salient features highly pertinent to aging are extracted from charge and discharge relaxation processes.By amalgamating historical capacity decay data,the model dynamically furnishes estimations of the present capacity and forecasts of future capacity for lithium-ion batteries.Our approach is validated against a novel dataset involving charge and discharge cycles at varying rates.Specifically,under a charging condition of 0.25 C,a mean absolute percentage error(MAPE)of 0.29%is achieved.This outcome underscores the model's adeptness in harnessing relaxation processes commonly encountered in the real world and synergizing with historical capacity records within battery management systems(BMS),thereby affording estimations and prognostications of capacity decline with heightened precision.

Effect of Surface Oxygen on Dissociation of Methane on Cu(100)

Clean and O-(2√2×√2)R45°Cu(100)surfaces were prepared to study the impact of surface oxygen on the activation of methane dissociation.Auger electron spectroscopy,low energy electron diffraction,infrared reflection absorption spectroscopy,scanning tunneling microscope,and a quadrupole mass-spectrometer for temperature programmed desorption were used to explore the behavior of CH_(4)on the two surfaces.The dissociative adsorption of CH_(4)was observed on oxygen-pre-covered Cu(100)but not on the clean surface indicating surface oxygen promotes the dissociation of the C-H bond.This study can be a reference for the conversion of methane into other high-value-added products with high efficiency and low energy consumption.

Data-Driven Viewpoint for Developing Next-Generation Mg-Ion Solid-State Electrolytes

Magnesium(Mg)is a promising alternative to lithium(Li)as an anode material in solid-state batteries due to its abundance and high theoretical volumetric capacity.However,the sluggish Mg-ion conduction in the lattice of solidstate electrolytes(SSEs)is one of the key challenges that hamper the development of Mg-ion solid-state batteries.Though various Mg-ion SSEs have been reported in recent years,key insights are hard to be derived from a single literature report.Besides,the structure-performance relationships of Mg-ion SSEs need to be further unraveled to provide a more precise design guideline for SSEs.In this viewpoint article,we analyze the structural characteristics of the Mg-based SSEs with high ionic conductivity reported in the last four decades based upon data mining-we provide big-data-derived insights into the challenges and opportunities in developing next-generation Mg-ion SSEs.

Model Order Reduction Methods for Discrete Systems via Discrete Pulse Orthogonal Functions

This paper explores model order reduction(MOR)methods for discrete linear and discrete bilinear systems via discrete pulse orthogonal functions(DPOFs).Firstly,the discrete linear systems and the discrete bilinear systems are expanded in the space spanned by DPOFs,and two recurrence formulas for the expansion coefficients of the system’s state variables are obtained.Then,a modified Arnoldi process is applied to both recurrence formulas to construct the orthogonal projection matrices,by which the reduced-order systems are obtained.Theoretical analysis shows that the output variables of the reducedorder systems can match a certain number of the expansion coefficients of the original system’s output variables.Finally,two numerical examples illustrate the feasibility and effectiveness of the proposed methods.

Cation effects in electrocatalytic reduction reactions:Recent advances

Electrocatalytic reduction reactions,powered by clean energy sources such as solar energy and wind,offer a sustainable method for converting inexpensive feedstocks(e.g.,CO_(2),N_(2)/NO_(x),organics,and O_(2))into high-value-added chemicals or fuels.The design and modification of electrocatalysts have been widely implemented to improve their performance in these reactions.However,bottle-necks are encountered,making it challenging to further improve performance through catalyst development alone.Recently,cations in the electrolyte have emerged as critical factors for tuning both the activity and product selectivity of reduction reactions.This review summarizes recent advances in understanding the role of cation effects in electrocatalytic reduction reactions.First,we introduce the mechanisms underlying cation effects.We then provide a comprehensive overview of their application in electroreduction reactions.Characterization techniques and theoretical calcula-tion methods for studying cation effects are also discussed.Finally,we address remaining challeng-es and future perspectives in this field.We hope that this review offers fundamental insights and design guidance for utilizing cation effects,thereby advancing their development.

Flotation separation of brucite and calcite in dodecylamine system enhanced by regulator potassium dihydrogen phosphate

To achieve efficient flotation separation of brucite and calcite,flotation separation experiments were conducted on two minerals using dodecylamine(DDA)as the collector and potassium dihydrogen phosphate(PDP)as the regulator.The action mechanism of DDA and PDP was explored through contact angle measurement,zeta potential detection,solution chemistry calculation,FTIR analysis,and XPS detection.The flotation results showed that when DDA dosage was 35 mg/L and PDP dosage was 40 mg/L,the maximum floating difference between brucite and calcite was 79.81%,and the selectivity separation index was 6.46.The detection analysis showed that the main dissolved component HPO_(4)^(2−)of PDP is selectively strongly adsorbed on the Ca site on the surface of calcite,promoting the adsorption of the main dissolved component RNH_(3)^(+)of DDA on calcite surface,while brucite is basically not affected by PDP.Therefore,PDP is an effective regulator for the reverse flotation separation of brucite and calcite in DDA system.

Pitch-derived soft carbon composite with hard carbon fibers for high-rate and long-cycling K^(+) storage

Potassium-ion batteries(KIBs)have been seen as a competitive alternative to lithium-ion batteries(LIBs)due to their natural abundance,low cost and rocking chair-like operating mechanism similar to LIBs.Soft carbon has a lower voltage plateau compared to hard carbon and an easily modulated lattice structure compared to graphite,which provides particular advantages in KIBs anodes.Pitch has attracted much attention as a simple,readily available and inexpensive precursor for soft carbon,but its structure is easily damaged during cycling.Herein,the flexible film Pitch@CNF are prepared by uniformly winding reticulated carbon fibers on the surface of pitch-soft carbon via electrostatic spinning technique,which not only enables the pitch to maintain its structure well during cycling and withstand the volume expansion upon K^(+) insertion,but also is conducive to ionic transport of the three-dimensional reticulated structure.Meanwhile,the abundant pores on the carbon fibers can provide more K^(+) active sites.The prepared flexible self-supporting films can be used directly as electrodes without the addition of binders and conductive agents.The reversible capacity is 290 mAh·g^(-1)at a current density of 0.1 A·g^(-1),and the capacity retention rate is 83%after 500 cycles.

Chalcogenide-based S-scheme heterojunction photocatalysts

The unique photocatalytic mechanism of S-scheme heterojunction can be used to study new and efficient photocatalysts.By carefully selecting semiconductors for S-scheme heterojunction photocatalysts,it is possible to reduce the rate of photogenerated carrier recombination and increase the conversion efficiency of light into energy.Chalcogenides are a group of compounds that include sulfides and selenides(e.g.,CdS,ZnS,Bi_(2)S_(3),MoS_(2),ZnSe,CdSe,and CuSe).Chalcogenides have attracted considerable attention as heterojunction photocatalysts owing to their narrow bandgap,wide light absorption range,and excellent photoreduction properties.This paper presents a thorough analysis of S-scheme heterojunction photocatalysts based on chalcogenides.Following an introduction to the fundamental characteristics and benefits of S-scheme heterojunction photocatalysts,various chalcogenide-based S-scheme heterojunction photocatalyst synthesis techniques are summarized.These photocatalysts are used in numerous significant photocatalytic reactions,in-cluding the reduction of carbon dioxide,synthesis of hydrogen peroxide,conversion of organic matter,generation of hydrogen from water,nitrogen fixation,degradation of organic pollutants,and sterilization.In addition,cutting-edge characterization techniques,including in situ characterization techniques,are discussed to validate the steady and transient states of photocatalysts with an S-scheme heterojunction.Finally,the design and challenges of chalcogenide-based S-scheme heterojunction photocatalysts are explored and recommended in light of state-of-the-art research.

Nitrogen⁃doped 3D graphene⁃carbon nanotube network for efficient lithium storage

A 3D nitrogen⁃doped graphene/multi⁃walled carbon nanotube(CS⁃GO⁃NCNT)crosslinked network mate⁃rial was successfully synthesized utilizing chitosan and melamine as carbon and nitrogen sources,concomitant with the incorporation of multi⁃wall carbon nanotubes and employing freeze drying technology.The material amalgamates the merits of 1D/2D hybrid carbon materials,wherein 1D carbon nanotubes confer robustness and expedited elec⁃tron transport pathways,while 2D graphene sheets facilitate rapid ion migration.Furthermore,the introduction of nitrogen heteroatoms serves to furnish additional active sites for lithium storage.When served as an anode material for lithium⁃ion batteries,the CS⁃GO⁃NCNT electrode delivered a reversible capacity surpassing 500 mAh·g^(-1),mark⁃edly outperforming commercial graphite anodes.Even after 300 cycles at a high current density of 1 A·g^(-1),it remained a reversible capacity of up to 268 mAh·g^(-1).

A novel immiscible high entropy alloy strengthened via L1_(2)-nanoprecipitate

The low-cost Fe-Cu,Fe-Ni,and Cu-based high-entropy alloys exhibit a widespread utilization prospect.However,these potential applications have been limited by their low strength.In this study,a novel Fe_(31)Cu_(31)Ni_(28)Al_(4)Ti_(3)Co_(3) immiscible high-entropy alloy(HEA)was developed.After vacuum arc melting and copper mold suction casting,this HEA exhibits a unique phase separation microstructure,which consists of striped Cu-rich regions and Fe-rich region.Further magnification of the striped Cu-rich region reveals that it is composed of a Cu-rich dot-like phase and a Fe-rich region.The aging alloy is further strengthened by a L1_(2)-Ni_(3)(AlTi)nanoprecipitates,achieving excellent yield strength(1185 MPa)and uniform ductility(~8.8%).The differential distribution of the L1_(2) nanoprecipitate in the striped Cu-rich region and the external Fe-rich region increased the strength difference between these two regions,which increased the strain gradient and thus improved hetero-deformation induced(HDI)hardening.This work provides a new route to improve the HDI hardening of Fe-Cu alloys.

First-Principles Study of Blue Phosphorene and Graphene Intralayer Heterostructure as Anode Materials for Rechargeable Li-lon Batteries

There is an ideal desire to develop the high-performance anodes materials for Liion batteries(LIBs),which requires not onlyhigh stability and reversibility,but also rapidcharging/discharging rate.In this work,webuiltablue phosphorene-graphene(BlueP-G)intralayer heterostructure by connecting BlueP and graphene monolayers at zigzag edges with covalent bonds.Based on the density functional theory simulation,the electronic structure of the heterostructure,Li adsorption and Li diffusion on heterostructure were systematically investigated.Compared with the pristine BlueP,the existence of graphene layer increases the overall conductivity of BlueP-G intralayer heterostructure.The significantly enhanced adsorption energy indicates the Li deposition on anode surface is energetically favored.The fast diffusion of Li with energy barrier as low as 0.02-0.09 eV indicates the growth of Li dendrite could be suppressed and the stability and reversibility of the battery will be increased.With a combination of increased conductivity of electronic charge,excellent Li adsorption and Li mobility on surface,BlueP-G intralayer heterostructure with zigzag interface is quite promising in the application of anode material for Li-ion batteries.

An efficient strategy for the preparation of MIL-53(Al)-NH_(2)membranes with high ion selectivity and desalination performance

The efficient extraction of sodium(Na^(+))and lithium(Li^(+))from seawater and salt lakes is increasingly demanding due to their great application value in chemical industries.However,coexisting cations such as divalent calcium(Ca^(2+))and magnesium(Mg^(2+))ions are at the subnanometer scale in diameter,similar to target monovalent ions,making ion separation a great challenge.Here,we propose a simple and fast secondary growth method for the preparation of MIL-53(Al)-NH_(2)membranes on the surface of anodic aluminum oxide.Such membranes contain angstrom-scale(~7Å)channels for the entrance of small monovalent ions and water molecules,endowing the selectivities for monovalent cations over divalent cations and water over salt molecules.The resulting high-connectivity MIL-53(Al)-NH_(2)membranes exhibit excellent ion separation performance(a selectivity of 121.42 for Na^(+)/Ca^(2+)and 93.81 for Li^(+)/Mg^(2+))and desalination performance(a water/salt selectivity of up to 5196).This work highlights metal–organic framework membranes as potential candidates for realizing ion separation and desalination in liquid treatment.

ZNT1 Involves Cuproptosis through Regulating MTF1-conduced Expression of MT1X under Copper Overload

Industrial activities such as smelting emissions,mineral combustion and industrial wastewater discharge might lead to copper pollution in the environment.This kind of copper pollution has harmful effects on aquatic o rganisms,plants and animals through direct or indirect exposure.However,the current understanding of the toxicity of copper is rather limited.Copper overload can perturb intracellular homeostasis and induce oxidative stress and e ven cell death.Recently,cuproptosis has been identified as a copper-dependent form of cell death induced by o xidative stress in mitochondria.We uncover here that zinc transporter 1(ZNT1)is an important regulator involved in cuproptosis.Firstly,we established the copper overload-induced cell death model with the overexpression of copper importer SLC31A1 in HeLa cells.Using this model,we conducted unbiased genome-wide CRISPR-Cas9 screens in cells treated with copper.Our results revealed a significant enrichment of ZNT1 gene in both library A and library B plasmids.Knocking out of ZNT1 in HeLa cells notably prevented cuproptosis.Subsequent knockout of metal transcription factor 1(MTF1)in ZNT1-deficient cells nearly abolished their ability to resist copper-induced cell death.However,overexpression of metallothionein 1X(MT1X)in the double-knockout cells could p artially restored the resistance to cuproptosis by loss of MTF1.Mechanistically,knockout of ZNT1 could promote MT1X expression by activating MTF1.As a consequence,the interaction between MT1X and copper was e nhanced,reducing the flow of copper into mitochondria and eliminating mitochondria damage.Taken together,this study reveals the important role of ZNT1 in cuproptosis and shows MTF1-MT1X axis mediated resistance to c uproptosis.Moreover,our study will help to understand the regulatory mechanism of cellular and systemic copper homeostasis under copper overload,and present insights into novel treatments for damages caused by both genetic copper overload diseases and environmental copper contamination.

The potassium storage performance of carbon nanosheets derived from heavy oils

As by-products of petroleum refining,heavy oils are characterized by a high carbon content,low cost and great variability,making them competitive precursors for the anodes of potassium ion batteries(PIBs).However,the relationship between heavy oil composition and potassium storage performance remains unclear.Using heavy oils containing distinct chemical groups as the carbon source,namely fluid catalytic cracking slurry(FCCS),petroleum asphalt(PA)and deoiled asphalt(DOA),three carbon nanosheets(CNS)were prepared through a molten salt method,and used as the anodes for PIBs.The composition of the heavy oil determines the lamellar thicknesses,sp3-C/sp2-C ratio and defect concentration,thereby affecting the potassium storage performance.The high content of aromatic hydrocarbons and moderate amount of heavy component moieties in FCCS produce carbon nanosheets(CNS-FCCS)that have a smaller layer thickness,larger interlayer spacing(0.372 nm),and increased number of folds than in CNS derived from the other three precursors.These features give it faster charge/ion transfer,more potassium storage sites and better reaction kinetics.CNS-FCCS has a remarkable K^(+)storage capacity(248.7 mAh g^(-1) after 100 cycles at 0.1 A g^(-1)),long cycle lifespan(190.8 mAh g^(-1) after 800 cycles at 1.0 A g^(-1))and excellent rate capability,ranking it among the best materials for this application.This work sheds light on the influence of heavy oil composition on carbon structure and electrochemical performance,and provides guidance for the design and development of advanced heavy oil-derived carbon electrodes for PIBs.

Separation of halogens and recovery of heavy metals from secondary copper smelting dust

The separation of halogens and recovery of heavy metals from secondary copper smelting(SCS)dust using a sulfating roasting−water leaching process were investigated.The thermodynamic analysis results confirm the feasibility of the phase transformation to metal sulfates and to gaseous HF and HCl.Under the sulfating roasting conditions of the roasting temperature of 250℃ and the sulfuric acid excess coefficient of 1.8,over 74 wt.%of F and 98 wt.%of Cl were volatilized into flue gas.Approximately 98.6 wt.%of Zn and 96.5 wt.%of Cu in the roasting product were dissolved into the leaching solution after the water leaching process,while the leaching efficiencies of Pb and Sn were only 0.12%and 0.22%,respectively.The mechanism studies indicate the pivotal effect of roasting temperature on the sulphation reactions from various metal species to metal sulfates and the salting out reactions from various metal halides to gaseous hydrogen halides.

Effects of anions on the structural regulation of Zn‑salen‑modified metal‑organic cage

By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-guest electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.

A review of the carbon coating of the silicon anode in highperformance lithium-ion batteries

In the development of rechargeable lithium ion batteries(LIBs),silicon anodes have attracted much attention because of their extremely high theoretical capacity,relatively low Li-insertion voltage and the availability of silicon resources.However,their large volume expansion and fragile solid electrolyte interface(SEI)film hinder their commercial application.To solve these problems,Si has been combined with various carbon materials to increase their structural stability and improve their interface properties.The use of different carbon materials,such as amorphous carbon and graphite,as three-dimensional(3D)protective anode coatings that help buffer mechanical strain and isolate the electrolyte is detailed,and novel methods for applying the coatings are outlined.However,carbon materials used as a protective layer still have some disadvantages,necessitating their modification.Recent developments have focused on modifying the protective carbon shells,and substitutes for the carbon have been suggested.

A review on the cooling of energy conversion and storage systems using thermoelectric modules

Exploitation of sustainable energy sources requires the use of unique conversion and storage systems,such as solar panels,batteries,fuel cells,and electronic equipment.Thermal load management of these energy conversion and storage systems is one of their challenges and concerns.In this article,the thermal management of these systems using thermoelectric modules is reviewed.The results show that by choosing the right option to remove heat from the hot side of the thermoelectric modules,it will be a suitable local cooling,and the thermoelectric modules increase the power and lifespan of the system by reducing the spot temperature.Thermoelectric modules were effective in reducing panel temperature.They increase the time to reach a temperature above 50℃ in batteries by 3 to 4 times.Also,in their integration with fuel cells,they increase the power density of the fuel cell.