Lithium–sulfur(Li–S) batteries have received widespread attention, and lean electrolyte Li–S batteries have attracted additional interest because of their higher energy densities. This review systematically analyze...Lithium–sulfur(Li–S) batteries have received widespread attention, and lean electrolyte Li–S batteries have attracted additional interest because of their higher energy densities. This review systematically analyzes the effect of the electrolyte-to-sulfur(E/S) ratios on battery energy density and the challenges for sulfur reduction reactions(SRR) under lean electrolyte conditions. Accordingly, we review the use of various polar transition metal sulfur hosts as corresponding solutions to facilitate SRR kinetics at low E/S ratios(< 10 μL mg~(-1)), and the strengths and limitations of different transition metal compounds are presented and discussed from a fundamental perspective. Subsequently, three promising strategies for sulfur hosts that act as anchors and catalysts are proposed to boost lean electrolyte Li–S battery performance. Finally, an outlook is provided to guide future research on high energy density Li–S batteries.展开更多
The influence of transition metals(Sc,Ti,V,Cr,and Mn)doping at different distances on the magnetism of CdS is studied by using generalized gradient approximation combined with Hubbard U in the VASP package.The results...The influence of transition metals(Sc,Ti,V,Cr,and Mn)doping at different distances on the magnetism of CdS is studied by using generalized gradient approximation combined with Hubbard U in the VASP package.The results show that the doping systems are more stable,easy to form,and the wurtzite structure of CdS is not changed.It is found that the systems are antiferromagnetic(AFM)when nearest neighbor doping,which is attributed to the direct charge transfers between two impurity ions.The systems are ferromagnetic(FM)when the doping distance increases further,since the double exchange interactions are observed among the 3d orbital of the transition metal,the Cd-5s and the S-3p orbitals are at conduction band minimum.We also found that the total magnetic moment of each ferromagnetic system increases with the order of SC to Mn-doping,the spin polarizability of Cr-doping system is 100%.The estimated Curie temperature indicates that the Cr-and Mn-doped CdS in this paper can achieve room-temperature ferromagnetic characteristics,especially the Cr doping is the most prominent.And TM-doping does not destroy the semiconductor characteristics of the system.Therefore,the TM-doped CdS can be used as an ideal dilute magnetic semiconductor functional material.展开更多
The catalytic activity of Perovskite-type mixed oxides (LaCoO3, PrCoO3 and SmCoO3) for the reduction of cyclohexanone to cyclohexanol with 2-propanol (Meerwein-PonndorfVerley reduction) has been studied. The data have...The catalytic activity of Perovskite-type mixed oxides (LaCoO3, PrCoO3 and SmCoO3) for the reduction of cyclohexanone to cyclohexanol with 2-propanol (Meerwein-PonndorfVerley reduction) has been studied. The data have been correlated with the surface electron donor properties of these mixed展开更多
The doping effects of transition metals(TMs = Mn, Co, Ni, and Cu) on the superconducting critical parameters are investigated in the films of iron selenide(Li,Fe)OHFe Se. The samples are grown via a matrix-assisted hy...The doping effects of transition metals(TMs = Mn, Co, Ni, and Cu) on the superconducting critical parameters are investigated in the films of iron selenide(Li,Fe)OHFe Se. The samples are grown via a matrix-assisted hydrothermal epitaxy method. Among the TMs, the elements of Mn and Co adjacent to Fe are observed to be incorporated into the crystal lattice more easily. It is suggested that the doped TMs mainly occupy the iron sites of the intercalated(Li,Fe)OH layers rather than those of the superconducting Fe Se layers. We find that the critical current density J_(c) can be enhanced much more strongly by the Mn dopant than the other TMs, while the critical temperature T_(c) is weakly affected by the TM doping.展开更多
Searching anodes with excellent electrochemical performance has been in great demand for rechargeable metal ion batteries. In this contribution, Fe/Co co-doped Ni S with N-based carbon(Fe Co-NiS@NC) derived from trime...Searching anodes with excellent electrochemical performance has been in great demand for rechargeable metal ion batteries. In this contribution, Fe/Co co-doped Ni S with N-based carbon(Fe Co-NiS@NC) derived from trimetallic Prussian blue analogue is designed and synthesized. The composition can be easily adjusted and modulated by multi-metals. In addition, the well-designed carbon nanocubes effectively promote electronic conductivity and buffer the volume change upon charge and discharge cycling, resulting in good capacity and long-term cycle life for both lithium-ion batteries and sodium-ion batteries, with capacities of 1018 m Ah g^(-1)(vs. Li/Li^(+)) and 454 m Ah g^(-1)(vs. Na/Na^(+)), respectively, after 100 cycles.Kinetics studies indicate that the electrochemical behaviors are manipulated by both diffusion and pseudocapacitance processes. These strategies would open new opportunities and potention for novel energy storage.展开更多
As the capacity of lithium-ion batteries gradually reaches its limit,the high-capacity characteristics of lithium metal batteries(LMBs)make them one of the most promising electrochemical energy storage devices current...As the capacity of lithium-ion batteries gradually reaches its limit,the high-capacity characteristics of lithium metal batteries(LMBs)make them one of the most promising electrochemical energy storage devices currently.However,uncontrolled lithium dendrite growth can cause poor cell performance and severe safety issues,seriously slowing down the commercialization of LMBs.Transition metals(TMs)are lithiophilic materials that effectively stabilize lithium metal anode(LMA)and inhibit dendrite growth.Herein,the growth of lithium dendrites and the performance of TMs in stabilizing lithium metals are comprehensively discussed in this review.First,we elucidated the formation mechanisms of lithium dendrite,and we put forward several strategies to suppress lithium dendrite formation based on the understanding of these mechanisms.Then,the application of TMs and their compounds to stabilize LMA and their corresponding mechanisms are comprehensively clarified.Last,further research perspectives of TMs in stabilizing LMA are emphasized in detail.展开更多
Ambient particulate matter(PM)can cause adverse health effects via their ability to produce Reactive Oxygen Species(ROS).Water-Soluble Organic Compounds(WSOCs),a complex mixture of organic compounds which usually coex...Ambient particulate matter(PM)can cause adverse health effects via their ability to produce Reactive Oxygen Species(ROS).Water-Soluble Organic Compounds(WSOCs),a complex mixture of organic compounds which usually coexist with Transition Metals(TMs)in PM,have been found to contribute to ROS formation.However,the interaction between WSOCs and TMs and its effect on ROS generation are still unknown.In this study,we examined the ROS concentrations of V,Zn,Suwannee River Fulvic Acid(SRFA),Suwannee River Humic Acid(SRHA)and the mixtures of V/Zn and SRFA/SRHA by using a cell-free 2’,7’-Dichlorodihydrofluorescein(DCFH)assay.The results showed that V or Zn synergistically promoted ROS generated by SRFA,but had an antagonistic effect on ROS generated by SRHA.Fluorescence quenching experiments indicated that V and Zn were more prone to form stable complexes with aromatic humic acid-like component(C1)and fulvic acidlike component(C3)in SRFA and SRHA.Results suggested that the underlying mechanism involving the fulvic acid-like component in SRFA more tending to complex with TMs to facilitate ROS generation throughπelectron transfer.Our work showed that the complexing ability and complexing stability of atmospheric PM organics with metals could significantly affect ROS generation.It is recommended that the research deploying multiple analytical methods to quantify the impact of PM components on public health and environment is needed in the future.展开更多
Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts...Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.展开更多
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 behav...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.展开更多
The laminated transition metal disulfides(TMDs),which are well known as typical two-dimensional(2D)semiconductive materials,possess a unique layered structure,leading to their wide-spread applications in various field...The laminated transition metal disulfides(TMDs),which are well known as typical two-dimensional(2D)semiconductive materials,possess a unique layered structure,leading to their wide-spread applications in various fields,such as catalysis,energy storage,sensing,etc.In recent years,a lot of research work on TMDs based functional materials in the fields of electromagnetic wave absorption(EMA)has been carried out.Therefore,it is of great significance to elaborate the influence of TMDs on EMA in time to speed up the application.In this review,recent advances in the development of electromagnetic wave(EMW)absorbers based on TMDs,ranging from the VIB group to the VB group are summarized.Their compositions,microstructures,electronic properties,and synthesis methods are presented in detail.Particularly,the modulation of structure engineering from the aspects of heterostructures,defects,morphologies and phases are systematically summarized,focusing on optimizing impedance matching and increasing dielectric and magnetic losses in the EMA materials with tunable EMW absorption performance.Milestones as well as the challenges are also identified to guide the design of new TMDs based dielectric EMA materials with high performance.展开更多
The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and ...The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.展开更多
Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review f...Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.展开更多
Mottness is at the heart of the essential physics in a strongly correlated system as many novel quantum phenomena occur in the metallic phase near the Mott metal–insulator transition. We investigate the Mott transiti...Mottness is at the heart of the essential physics in a strongly correlated system as many novel quantum phenomena occur in the metallic phase near the Mott metal–insulator transition. We investigate the Mott transition in a Hubbard model by using the dynamical mean-field theory and introduce the local quantum state fidelity to depict the Mott metal–insulator transition. The local quantum state fidelity provides a convenient approach to determining the critical point of the Mott transition. Additionally, it presents a consistent description of the two distinct forms of the Mott transition points.展开更多
Mg2+in MgAl-layered double hydroxides nanoparticles was substituted with different divalent transition metal ions(MAl-LDHs,M:Mg2+,Cu2+,Ni2+,Co2+,and Mn2+)via a facile method to be used as antibacterial agents.The phas...Mg2+in MgAl-layered double hydroxides nanoparticles was substituted with different divalent transition metal ions(MAl-LDHs,M:Mg2+,Cu2+,Ni2+,Co2+,and Mn2+)via a facile method to be used as antibacterial agents.The phase structural and morphological characterizations of MAl-LDHs were investigated by XRD,FTIR spectroscopy and TEM.The results have shown that all of MAl-LDHs had typical layered structures except MnAl-LDH which contained Mn304 phases.Particular morphology of MnAl-LDH with ellipsoids,spherical and rod-like structure and CuAl-LDH with rod-like shape existed.IC50(the concentrations providing 50%antibacterial activity)values of CuAl-LDH,NiAl-LDH,CoAl-LDH,and MnAlLDH in broth dilution tests were^800-1500μg/mL.Dosages of CuAl-LDH,CoAl-LDH,and MnAl-LDH with>10 mm inhibition zone in disk diffusion tests were^150-300μg/disk.Antibacterial mechanism of MAl-LDHs may be attributed to the synergistic factors including effected surroundings,surface interactions,morphology of particles,ROS and metal ions.The results indicate a facile method to synthesis LDHs based effective antibacterial agents with the potential application in the area of water treatment and antibacterial coating.展开更多
Microwave irradiation is considered an important approach to Green Chemistry, because of its ability to rapidly increase the internal temperature of polar-organic compounds that lead to synthesis times of minutes rath...Microwave irradiation is considered an important approach to Green Chemistry, because of its ability to rapidly increase the internal temperature of polar-organic compounds that lead to synthesis times of minutes rather than hours when compared to conventional thermal heating. This works describes a dual allometry test for the discrimination between the solvents and reagents used in the microwave-assisted synthesis of transition metal (zinc oxide, palladium silver, platinum, and gold) nanostructures. The test is performed in log-log process energy phase-space projection, where the synthesis data (kJ against kJ·mol<sup>-1</sup>) has a power-law signature. The test is shown to discriminate between recommended Green Chemistry, problematic Green Chemistry, and Green Chemistry hazardous solvents. Typically, recommended Green chemistry exhibits a broad y-axes distribution within an upper exponent = 1 and lower exponent = 0.5. Problematic Green Chemistry exhibits a y-axes narrower distribution with an upper exponent = 0.94 and lower exponent = 0.64. Non-Green Chemistry hazardous data exhibits a further narrowing of the y-axes distribution within upper exponent = 0.87 and lower exponent = 0.66. In all three cases, the y-axes is aligned to original database power-law signature. It is also shown that in the x-axes direction (process energy budget) the grouped order of magnitude decreases from four orders for recommended Green Chemistry solvent and reagent data, through two orders for non-Green Chemistry hazardous material and down to one order for problematic Green Chemistry.展开更多
The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in ab...The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.展开更多
A condition for local moment formation in metals derived by Stoddart and March (Ann. Phys. NY 1972 64, 174) is first used to discuss the ferromagnetism of body-centred-cubic Fe. A less detailed discussion is also adde...A condition for local moment formation in metals derived by Stoddart and March (Ann. Phys. NY 1972 64, 174) is first used to discuss the ferromagnetism of body-centred-cubic Fe. A less detailed discussion is also added on Ni and Co. This leads into a treatment of the non- linear response of such 3d ferromagnets to dilute substitutional impurities. Antiferromagnets responding to local changes in the exchange field caused by such impurities are also studied, Mn in Cr being one such system discussed. The paper concludes with a brief summary of clusters of transition metal atoms, with most attention devoted to Cr and to Mn.展开更多
Transition metal dichalcogenides(TMDs)show great advantages in electromagnetic wave(EMW)absorption due to their unique structure and electrical properties.Tremendous research works on TMD-based EMW absorbers have been...Transition metal dichalcogenides(TMDs)show great advantages in electromagnetic wave(EMW)absorption due to their unique structure and electrical properties.Tremendous research works on TMD-based EMW absorbers have been conducted in the last three years,and the comprehensive and systematical summary is still a rarity.Therefore,it is of great significance to elaborate on the interaction among the morphologies,structures,phases,components,and EMW absorption performances of TMD-based absorbers.This review is devoted to analyzing TMD-based absorbers from the following perspectives:the EMW absorption regulation strategies of TMDs and the latest progress of TMD-based hybrids as EMW absorbers.The absorption mechanisms and component-performance dependency of these achievements are also summarized.Finally,a straightforward insight into industrial revolution upgrading in this promising field is proposed.展开更多
Electrocatalytic oxygen evolution reaction(OER)has been recognized as the bottleneck of overall water splitting,which is a promising approach for sustainable production of H_(2).Transition metal(TM)hydroxides are the ...Electrocatalytic oxygen evolution reaction(OER)has been recognized as the bottleneck of overall water splitting,which is a promising approach for sustainable production of H_(2).Transition metal(TM)hydroxides are the most conventional and classical non-noble metal-based electrocatalysts for OER,while TM basic salts[M^(2+)(OH)_(2-x)(A_(m^(-))_(x/m),A=CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)]consisting of OH−and another anion have drawn extensive research interest due to its higher catalytic activity in the past decade.In this review,we summarize the recent advances of TM basic salts and their application in OER and further overall water splitting.We categorize TM basic salt-based OER pre-catalysts into four types(CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)according to the anion,which is a key factor for their outstanding performance towards OER.We highlight experimental and theoretical methods for understanding the structure evolution during OER and the effect of anion on catalytic performance.To develop bifunctional TM basic salts as catalyst for the practical electrolysis application,we also review the present strategies for enhancing its hydrogen evolution reaction activity and thereby improving its overall water splitting performance.Finally,we conclude this review with a summary and perspective about the remaining challenges and future opportunities of TM basic salts as catalysts for water electrolysis.展开更多
The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are u...The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.展开更多
基金the Research Foundation-Flanders (FWO) for a Research Project (G0B3218N)the financial support by the National Natural Science Foundation of China (22005054)+3 种基金Natural Science Foundation of Fujian Province (2021J01149)State Key Laboratory of Structural Chemistry (20200007)Sichuan Science and Technology Program (project No.: 2022ZYD0016 and 2023JDRC0013)the National Natural Science Foundation of China (project No. 21776120)。
文摘Lithium–sulfur(Li–S) batteries have received widespread attention, and lean electrolyte Li–S batteries have attracted additional interest because of their higher energy densities. This review systematically analyzes the effect of the electrolyte-to-sulfur(E/S) ratios on battery energy density and the challenges for sulfur reduction reactions(SRR) under lean electrolyte conditions. Accordingly, we review the use of various polar transition metal sulfur hosts as corresponding solutions to facilitate SRR kinetics at low E/S ratios(< 10 μL mg~(-1)), and the strengths and limitations of different transition metal compounds are presented and discussed from a fundamental perspective. Subsequently, three promising strategies for sulfur hosts that act as anchors and catalysts are proposed to boost lean electrolyte Li–S battery performance. Finally, an outlook is provided to guide future research on high energy density Li–S batteries.
基金Project supported by the National Natural Science Foundation of China (Grant No. 11664023)the Hong Liu First-class Disciplines Development Program of Lanzhou University of TechnologyState Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals of China
文摘The influence of transition metals(Sc,Ti,V,Cr,and Mn)doping at different distances on the magnetism of CdS is studied by using generalized gradient approximation combined with Hubbard U in the VASP package.The results show that the doping systems are more stable,easy to form,and the wurtzite structure of CdS is not changed.It is found that the systems are antiferromagnetic(AFM)when nearest neighbor doping,which is attributed to the direct charge transfers between two impurity ions.The systems are ferromagnetic(FM)when the doping distance increases further,since the double exchange interactions are observed among the 3d orbital of the transition metal,the Cd-5s and the S-3p orbitals are at conduction band minimum.We also found that the total magnetic moment of each ferromagnetic system increases with the order of SC to Mn-doping,the spin polarizability of Cr-doping system is 100%.The estimated Curie temperature indicates that the Cr-and Mn-doped CdS in this paper can achieve room-temperature ferromagnetic characteristics,especially the Cr doping is the most prominent.And TM-doping does not destroy the semiconductor characteristics of the system.Therefore,the TM-doped CdS can be used as an ideal dilute magnetic semiconductor functional material.
文摘The catalytic activity of Perovskite-type mixed oxides (LaCoO3, PrCoO3 and SmCoO3) for the reduction of cyclohexanone to cyclohexanol with 2-propanol (Meerwein-PonndorfVerley reduction) has been studied. The data have been correlated with the surface electron donor properties of these mixed
基金Project supported by the National Key Research and Development Program of China(Grant Nos.2017YFA0303003 and 2016YFA0300300)the National Natural Science Foundation of China(Grant Nos.11834016 and 11888101)+1 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(Grant Nos.XDB33010200 and XDB25000000)the Strategic Priority Research Program and Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(Grant Nos.QYZDY-SSW-SLH001 and QYZDY-SSW-SLH008)。
文摘The doping effects of transition metals(TMs = Mn, Co, Ni, and Cu) on the superconducting critical parameters are investigated in the films of iron selenide(Li,Fe)OHFe Se. The samples are grown via a matrix-assisted hydrothermal epitaxy method. Among the TMs, the elements of Mn and Co adjacent to Fe are observed to be incorporated into the crystal lattice more easily. It is suggested that the doped TMs mainly occupy the iron sites of the intercalated(Li,Fe)OH layers rather than those of the superconducting Fe Se layers. We find that the critical current density J_(c) can be enhanced much more strongly by the Mn dopant than the other TMs, while the critical temperature T_(c) is weakly affected by the TM doping.
基金supported by the National Natural Science Foundation of China(Grant Nos.21974007 and 22090043)。
文摘Searching anodes with excellent electrochemical performance has been in great demand for rechargeable metal ion batteries. In this contribution, Fe/Co co-doped Ni S with N-based carbon(Fe Co-NiS@NC) derived from trimetallic Prussian blue analogue is designed and synthesized. The composition can be easily adjusted and modulated by multi-metals. In addition, the well-designed carbon nanocubes effectively promote electronic conductivity and buffer the volume change upon charge and discharge cycling, resulting in good capacity and long-term cycle life for both lithium-ion batteries and sodium-ion batteries, with capacities of 1018 m Ah g^(-1)(vs. Li/Li^(+)) and 454 m Ah g^(-1)(vs. Na/Na^(+)), respectively, after 100 cycles.Kinetics studies indicate that the electrochemical behaviors are manipulated by both diffusion and pseudocapacitance processes. These strategies would open new opportunities and potention for novel energy storage.
基金supported by National Natural Science Foundation of China (No.22005172)Natural Science Foundation of Sichuan Province (No.2023NSFSC1124)+1 种基金Fundamental Research Funds for the Central Universities (No.YJ2021141)the Science and Technology Cooperation Special Fund of Sichuan University and Zigong City (No.2022CDZG-9)。
文摘As the capacity of lithium-ion batteries gradually reaches its limit,the high-capacity characteristics of lithium metal batteries(LMBs)make them one of the most promising electrochemical energy storage devices currently.However,uncontrolled lithium dendrite growth can cause poor cell performance and severe safety issues,seriously slowing down the commercialization of LMBs.Transition metals(TMs)are lithiophilic materials that effectively stabilize lithium metal anode(LMA)and inhibit dendrite growth.Herein,the growth of lithium dendrites and the performance of TMs in stabilizing lithium metals are comprehensively discussed in this review.First,we elucidated the formation mechanisms of lithium dendrite,and we put forward several strategies to suppress lithium dendrite formation based on the understanding of these mechanisms.Then,the application of TMs and their compounds to stabilize LMA and their corresponding mechanisms are comprehensively clarified.Last,further research perspectives of TMs in stabilizing LMA are emphasized in detail.
基金supported by the Fundamental Research Funds for the Central Universities (No. E0E48927X2)the National Natural Science Foundation of China (No. 21677145)
文摘Ambient particulate matter(PM)can cause adverse health effects via their ability to produce Reactive Oxygen Species(ROS).Water-Soluble Organic Compounds(WSOCs),a complex mixture of organic compounds which usually coexist with Transition Metals(TMs)in PM,have been found to contribute to ROS formation.However,the interaction between WSOCs and TMs and its effect on ROS generation are still unknown.In this study,we examined the ROS concentrations of V,Zn,Suwannee River Fulvic Acid(SRFA),Suwannee River Humic Acid(SRHA)and the mixtures of V/Zn and SRFA/SRHA by using a cell-free 2’,7’-Dichlorodihydrofluorescein(DCFH)assay.The results showed that V or Zn synergistically promoted ROS generated by SRFA,but had an antagonistic effect on ROS generated by SRHA.Fluorescence quenching experiments indicated that V and Zn were more prone to form stable complexes with aromatic humic acid-like component(C1)and fulvic acidlike component(C3)in SRFA and SRHA.Results suggested that the underlying mechanism involving the fulvic acid-like component in SRFA more tending to complex with TMs to facilitate ROS generation throughπelectron transfer.Our work showed that the complexing ability and complexing stability of atmospheric PM organics with metals could significantly affect ROS generation.It is recommended that the research deploying multiple analytical methods to quantify the impact of PM components on public health and environment is needed in the future.
基金the support from the CIPHER Project(IIID 2018-008)funded by the Commission on Higher Education-Philippine California Advanced Research Institutes(CHED-PCARI)。
文摘Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.
基金This work was supported by National Key R&D Program of China(2021YFF1200200)Peiyang Talents Project of Tianjin University.
文摘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.
基金This work was supported by the National Natural Science Foundation of China(52372289,52102368,52072192 and 51977009)Regional Joint Fund for Basic Research and Applied Basic Research of Guangdong Province(No.2020SA001515110905).
文摘The laminated transition metal disulfides(TMDs),which are well known as typical two-dimensional(2D)semiconductive materials,possess a unique layered structure,leading to their wide-spread applications in various fields,such as catalysis,energy storage,sensing,etc.In recent years,a lot of research work on TMDs based functional materials in the fields of electromagnetic wave absorption(EMA)has been carried out.Therefore,it is of great significance to elaborate the influence of TMDs on EMA in time to speed up the application.In this review,recent advances in the development of electromagnetic wave(EMW)absorbers based on TMDs,ranging from the VIB group to the VB group are summarized.Their compositions,microstructures,electronic properties,and synthesis methods are presented in detail.Particularly,the modulation of structure engineering from the aspects of heterostructures,defects,morphologies and phases are systematically summarized,focusing on optimizing impedance matching and increasing dielectric and magnetic losses in the EMA materials with tunable EMW absorption performance.Milestones as well as the challenges are also identified to guide the design of new TMDs based dielectric EMA materials with high performance.
文摘The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.
基金The authors acknowledge funding from National Natural Science Foundation of China(52302307)Shaanxi Province(2023-ZDLGY-24,2023-JC-QN-0473)+2 种基金project funded by China Postdoctoral Science Foundation(2023MD734210)the Open Foundation of State Key Laboratory for Advanced Metals and Materials(2022-Z01)Shaanxi Provincial Department of Education industrialization project(21JC018).
文摘Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.
基金Project supported by the Scientific Research Foundation for Youth Academic Talent of Inner Mongolia University (Grant No.1000023112101/010)the Fundamental Research Funds for the Central Universities of China (Grant No.JN200208)+2 种基金supported by the National Natural Science Foundation of China (Grant No.11474023)supported by the National Key Research and Development Program of China (Grant No.2021YFA1401803)the National Natural Science Foundation of China (Grant Nos.11974051 and 11734002)。
文摘Mottness is at the heart of the essential physics in a strongly correlated system as many novel quantum phenomena occur in the metallic phase near the Mott metal–insulator transition. We investigate the Mott transition in a Hubbard model by using the dynamical mean-field theory and introduce the local quantum state fidelity to depict the Mott metal–insulator transition. The local quantum state fidelity provides a convenient approach to determining the critical point of the Mott transition. Additionally, it presents a consistent description of the two distinct forms of the Mott transition points.
基金financially supported by Advance Queensland Research Fellowship Project and Chinese Scholarship Council(CSC)。
文摘Mg2+in MgAl-layered double hydroxides nanoparticles was substituted with different divalent transition metal ions(MAl-LDHs,M:Mg2+,Cu2+,Ni2+,Co2+,and Mn2+)via a facile method to be used as antibacterial agents.The phase structural and morphological characterizations of MAl-LDHs were investigated by XRD,FTIR spectroscopy and TEM.The results have shown that all of MAl-LDHs had typical layered structures except MnAl-LDH which contained Mn304 phases.Particular morphology of MnAl-LDH with ellipsoids,spherical and rod-like structure and CuAl-LDH with rod-like shape existed.IC50(the concentrations providing 50%antibacterial activity)values of CuAl-LDH,NiAl-LDH,CoAl-LDH,and MnAlLDH in broth dilution tests were^800-1500μg/mL.Dosages of CuAl-LDH,CoAl-LDH,and MnAl-LDH with>10 mm inhibition zone in disk diffusion tests were^150-300μg/disk.Antibacterial mechanism of MAl-LDHs may be attributed to the synergistic factors including effected surroundings,surface interactions,morphology of particles,ROS and metal ions.The results indicate a facile method to synthesis LDHs based effective antibacterial agents with the potential application in the area of water treatment and antibacterial coating.
文摘Microwave irradiation is considered an important approach to Green Chemistry, because of its ability to rapidly increase the internal temperature of polar-organic compounds that lead to synthesis times of minutes rather than hours when compared to conventional thermal heating. This works describes a dual allometry test for the discrimination between the solvents and reagents used in the microwave-assisted synthesis of transition metal (zinc oxide, palladium silver, platinum, and gold) nanostructures. The test is performed in log-log process energy phase-space projection, where the synthesis data (kJ against kJ·mol<sup>-1</sup>) has a power-law signature. The test is shown to discriminate between recommended Green Chemistry, problematic Green Chemistry, and Green Chemistry hazardous solvents. Typically, recommended Green chemistry exhibits a broad y-axes distribution within an upper exponent = 1 and lower exponent = 0.5. Problematic Green Chemistry exhibits a y-axes narrower distribution with an upper exponent = 0.94 and lower exponent = 0.64. Non-Green Chemistry hazardous data exhibits a further narrowing of the y-axes distribution within upper exponent = 0.87 and lower exponent = 0.66. In all three cases, the y-axes is aligned to original database power-law signature. It is also shown that in the x-axes direction (process energy budget) the grouped order of magnitude decreases from four orders for recommended Green Chemistry solvent and reagent data, through two orders for non-Green Chemistry hazardous material and down to one order for problematic Green Chemistry.
文摘The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.
文摘A condition for local moment formation in metals derived by Stoddart and March (Ann. Phys. NY 1972 64, 174) is first used to discuss the ferromagnetism of body-centred-cubic Fe. A less detailed discussion is also added on Ni and Co. This leads into a treatment of the non- linear response of such 3d ferromagnets to dilute substitutional impurities. Antiferromagnets responding to local changes in the exchange field caused by such impurities are also studied, Mn in Cr being one such system discussed. The paper concludes with a brief summary of clusters of transition metal atoms, with most attention devoted to Cr and to Mn.
基金financially supported by the Doctoral Foundation of Henan University of Technology(No.2021BS030)Natural Science Foundation of Shandong Province(No.ZR2019YQ24)+1 种基金Taishan Scholars and Young Experts Program of Shandong Province(No.tsqn202103057)Qingchuang Talents Induction Program of Shandong Higher Education Institution(Research and Innovation Team of Structural-Functional Polymer Composites)。
文摘Transition metal dichalcogenides(TMDs)show great advantages in electromagnetic wave(EMW)absorption due to their unique structure and electrical properties.Tremendous research works on TMD-based EMW absorbers have been conducted in the last three years,and the comprehensive and systematical summary is still a rarity.Therefore,it is of great significance to elaborate on the interaction among the morphologies,structures,phases,components,and EMW absorption performances of TMD-based absorbers.This review is devoted to analyzing TMD-based absorbers from the following perspectives:the EMW absorption regulation strategies of TMDs and the latest progress of TMD-based hybrids as EMW absorbers.The absorption mechanisms and component-performance dependency of these achievements are also summarized.Finally,a straightforward insight into industrial revolution upgrading in this promising field is proposed.
基金supported by the financial support from Natural Science Foundation of China(Nos.21871065,22209129 and 22071038)High-Level Innovation and Entrepreneurship(QCYRCXM-2022-123)+1 种基金support from the“Young Talent Support Plan”of Xi’an Jiaotong University(HG6J024)“Young Talent Lift Plan”of Xi’an city(095920221352).
文摘Electrocatalytic oxygen evolution reaction(OER)has been recognized as the bottleneck of overall water splitting,which is a promising approach for sustainable production of H_(2).Transition metal(TM)hydroxides are the most conventional and classical non-noble metal-based electrocatalysts for OER,while TM basic salts[M^(2+)(OH)_(2-x)(A_(m^(-))_(x/m),A=CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)]consisting of OH−and another anion have drawn extensive research interest due to its higher catalytic activity in the past decade.In this review,we summarize the recent advances of TM basic salts and their application in OER and further overall water splitting.We categorize TM basic salt-based OER pre-catalysts into four types(CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)according to the anion,which is a key factor for their outstanding performance towards OER.We highlight experimental and theoretical methods for understanding the structure evolution during OER and the effect of anion on catalytic performance.To develop bifunctional TM basic salts as catalyst for the practical electrolysis application,we also review the present strategies for enhancing its hydrogen evolution reaction activity and thereby improving its overall water splitting performance.Finally,we conclude this review with a summary and perspective about the remaining challenges and future opportunities of TM basic salts as catalysts for water electrolysis.
基金Y.C.and J.C.are contributed equally to the paper.Project supported by the National Natural Science Foundation of China (U19A2017)the Fundamental Research Funds for the Central South University and the Australian Research Council (DP180100731 and DP180100568)。
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.
