Research progress of alkaline earth metal iron-based oxides as anodes for lithium-ion batteries

Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.

An effective strategy of constructing multi-metallic oxides of ZnO/ CoNiO_(2)/CoO/C microflowers for improved supercapacitive performance

In this work,a new ZnO/CoNiO_(2)/CoO/C metal oxides composite is prepared by cost-effective hydrothermal method coupled with annealing process under N_(2) atmosphere.Notably,the oxidation-defect annealing environment is conducive to both morphology and component of the composite,which flower-like ZnO/CoNiO_(2)/CoO/C is obtained.Benefited from good chemical stability of ZnO,high energy capacity of CoNiO_(2) and CoO and good conductivity of C,the as-prepared sample shows promising electrochemical behavior,including the specific capacity of 1435 C·g^(-1) at 1 A·g^(-1),capacity retention of 87.3%at 20 A·g^(-1),and cycling stability of 90.5%for 3000 cycles at 5 A·g^(-1),respectively.Furthermore,the prepared ZnO/CoNiO_(2)/CoO/C/NF//AC aqueous hybrid supercapacitors device delivers the best specific energy of 55.9 W·h·kg^(-1) at 850 W·kg^(-1).The results reflect that the as-prepared ZnO/CoNiO_(2)/CoO/C microflowers are considered as high performance electrode materials for supercapacitor,and the strategy mentioned in this paper is benefit to prepare mixed metal oxides composite for energy conversion and storage.

Revealing the correlation between adsorption energy and activation energy to predict the catalytic activity of metal oxides for HMX using DFT

Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost.

A critical review towards the causes of the iron-based catalysts deactivation mechanisms in the selective oxidation of hydrogen sulfide to elemental sulfur from biogas

Hydrogen sulfide(H_(2)S) not only presents significant environmental concerns but also induces severe corrosion in industrial equipment,even at low concentrations.Among various technologies,the selective oxidation of hydrogen sulfide(SOH_(2)S) to elemental sulfur(S) has emerged as a sustainable and environmentally friendly solution.Due to its unique properties,iron oxide has been extensively investigated as a catalyst for SOH_(2)S;however,rapid deactivation has remained a significant drawback.The causes of iron oxide-based catalysts deactivation mechanisms in SOH_(2)S,including sulfur or sulfate deposition,the transformation of iron species,sintering and excessive oxygen vacancy formation,and active site loss,are thoroughly examined in this review.By focusing on the deactivation mechanisms,this review aims to provide valuable insights into enhancing the stability and efficiency of iron-based catalysts for SOH_(2)S.

Highly dispersed MgInCe-mixed metal oxides catalyzed direct carbonylation of glycerol and CO_(2)into glycerol carbonate

Glycerol carbonate,an important glycerol value-added product,has been widely used as an active intermediate and inert solvent in the synthesis of cosmetics,detergents,chemical intermediates,polymers,and so on.The direct carbonylation from glycerol with CO_(2)is considered a promising route,but still tough work due to the thermodynamic stability and the kinetic inertness of CO_(2).In this work,highlyselective direct carbonylation of glycerol and CO_(2)into glycerol carbonate has been achieved over highly dispersed MgInCe-mixed metal oxides(MgInCe-MMO),which were prepared through the topological transformation derived from the MgInCe-layered double hydroxides(MgInCe-LDHs).By precisely modulating the surface basic-acidic properties and the oxygen vacancies,an efficient carbonylation of glycerol with CO_(2)has been achieved with a selectivity of up to>99%to glycerol carbonate.Deep investigation into the synergistic catalysis of base-acid sites and oxygen vacancies has been clarified.

A review of ^(17)O isotopic labeling techniques for solid-state NMR structural studies of metal oxides in lithium-ion batteries

Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.

Laser‑Induced and MOF‑Derived Metal Oxide/Carbon Composite for Synergistically Improved Ethanol Sensing at Room temperature

Advancements in sensor technology have significantly enhanced atmospheric monitoring.Notably,metal oxide and carbon(MO_(x)/C)hybrids have gained attention for their exceptional sensitivity and room-temperature sensing performance.However,previous methods of synthesizing MO_(x)/C composites suffer from problems,including inhomogeneity,aggregation,and challenges in micropatterning.Herein,we introduce a refined method that employs a metal–organic framework(MOF)as a precursor combined with direct laser writing.The inherent structure of MOFs ensures a uniform distribution of metal ions and organic linkers,yielding homogeneous MO_(x)/C structures.The laser processing facilitates precise micropatterning(<2μm,comparable to typical photolithography)of the MO_(x)/C crystals.The optimized MOF-derived MO_(x)/C sensor rapidly detected ethanol gas even at room temperature(105 and 18 s for response and recovery,respectively),with a broad range of sensing performance from 170 to 3,400 ppm and a high response value of up to 3,500%.Additionally,this sensor exhibited enhanced stability and thermal resilience compared to previous MOF-based counterparts.This research opens up promising avenues for practical applications in MOF-derived sensing devices.

Photoelectrochemical seawater oxidation with metal oxide materials:Challenges and opportunities

Photocatalytic water oxidation is a crucial counter-electrode reaction in the process of photoelectrochemical energy conversion.Despite its importance,challenges remain in effectively and sustainably converting water to oxygen,particularly with readily available and inexpensive electrolyte solutions such as seawater.While metal oxide materials have demonstrated their advantages in promoting efficiency by reducing overpotential and improving light utilization,stability remains limited by corrosion in multicomponent seawater.In this paper,we reviewed the relationship between four basic concepts including photoelectrochemistry,metal oxide,water oxidation and seawater to better understand the challenges and opportunities in photoelectrochemical(PEC)seawater oxidation.To overcome these challenges,the advances in material design,interfacial modification,local environment control and reactor design have been further reviewed to benefit the industrial PEC seawater oxidation.Noticeably,we demonstrate engineered layered metal oxide electrodes and cell structures that enable powerful and stable seawater oxidation.We also outline and advise on the future direction in this area.

Progress in metal oxide-based electrocatalysts for sustainable water splitting

Metal oxide-based electrocatalysts are promising alternatives to platinum group metals for water splitting due to their low cost,abundant raw materials,and impressive stability.This review covers recent progress in various metal oxides tailored for hydrogen and oxygen evolution reactions,discussing their crystal structure,composition,and surface modification influence on performance.Strategies like surface engineering,doping,and nanostructuring are evaluated for enhancing catalytic activity and stability.The key considerations for commercialization are highlighted,emphasizing ongoing research,innovation,and future scope to drive widespread adoption of water-splitting technology for a cleaner and sustainable future.

3D printing of poly(ethyleneimine)-functionalized Mg-Al mixed metal oxide monoliths for direct air capture of CO_(2)

Direct air capture(DAC)of CO_(2)plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies.Since large air flows are required to capture the ultradilute CO_(2)from the air,lab-synthesized adsorbents in powder form may cause unacceptable gas pressure drops and poor heat and mass transfer efficiencies.A structured adsorbent is essential for the implementation of gas-solid contactors for cost-and energy-efficient DAC systems.In this study,efficient adsorbent poly(ethyleneimine)(PEI)-functionalized Mg-Al-CO_(3)layered double hydroxide(LDH)-derived mixed metal oxides(MMOs)are three-dimensional(3D)printed into monoliths for the first time with more than 90%adsorbent loadings.The printing process has been optimized by initially printing the LDH powder into monoliths followed by calcination into MMO monoliths.This structure exhibits a 32.7%higher specific surface area and a 46.1%higher pore volume,as compared to the direct printing of the MMO powder into a monolith.After impregnation of PEI,the monolith demonstrates a large adsorption capacity(1.82 mmol/g)and fast kinetics(0.7 mmol/g/h)using a CO_(2)feed gas at 400 ppm at 25℃,one of the highest values among the shaped DAC adsorbents.Smearing of the amino-polymers during the post-printing process affects the diffusion of CO_(2),resulting in slower adsorption kinetics of pre-impregnation monoliths compared to post-impregnation monoliths.The optimal PEI/MeOH ratio for the post-impregnation solution prevents pores clogging that would affect both adsorption capacity and kinetics.

Metal oxides heterojunction derived Bi-In hybrid electrocatalyst for robust electroreduction of CO_(2) to formate

Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity at high current density is important for formate production,but remains challenging.Herein,the BiIn hybrid electrocatalyst,deriving from the Bi2O3/In2O3heterojunction(MOD-Biln),shows excellent catalytic performance for CO_(2)RR.The Faradaic efficiency of formate(FEHCOO-) can be realized over 90% at a wide potential window from-0.4 to-1.4 V vs.RHE,while the partial current density of formate(jHCOO-) reaches about 136.7 mA cm^(-2)at-1.4 V in flow cell without IR-compensation.In additio n,the MOD-Biln exhibits superior stability with high selectivity of formate at 100 mA cm^(-2).Systematic characterizations prove the optimized catalytic sites and interface charge transfer of MOD-Biln,while theoretical calculation confirms that the hybrid structure with dual Bi/In metal sites contribute to the optimal free energy of*H and*OCHO intermediates on MOD-Biln surface,thus accelerating the formation and desorption step of*HCOOH to final formate production.Our work provides a facile and useful strategy to develop highly-active and stable electrocatalysts for CO_(2)RR.

Fast and Balanced Charge Transport Enabled by Solution-Processed Metal Oxide Layers for Efficient and Stable Inverted Perovskite Solar Cells

Metal oxide charge transport materials are preferable for realizing long-term stable and potentially low-cost perovskite solar cells(PSCs).However,due to some technical difficulties(e.g.,intricate fabrication protocols,high-temperature heating process,incompatible solvents,etc.),it is still challenging to achieve efficient and reliable all-metal-oxide-based devices.Here,we developed efficient inverted PSCs(IPSCs)based on solution-processed nickel oxide(NiO_(x))and tin oxide(SnO_(2))nanoparticles,working as hole and electron transport materials respectively,enabling a fast and balanced charge transfer for photogenerated charge carriers.Through further understanding and optimizing the perovskite/metal oxide interfaces,we have realized an outstanding power conversion efficiency(PCE)of 23.5%(the bandgap of the perovskite is 1.62 eV),which is the highest efficiency among IPSCs based on all-metal-oxide charge transport materials.Thanks to these stable metal oxides and improved interface properties,ambient stability(retaining 95%of initial PCE after 1 month),thermal stability(retaining 80%of initial PCE after 2 weeks)and light stability(retaining 90%of initial PCE after 1000 hours aging)of resultant devices are enhanced significantly.In addition,owing to the low-temperature fabrication procedures of the entire device,we have obtained a PCE of over 21%for flexible IPSCs with enhanced operational stability.

Screening non-noble metal oxides to boost the low-temperature combustion of polyethylene waste in air

Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal with polymer wastes and recover heat energy,simultaneously alleviating the environment and energy crisis.Non-noble metal oxides(Al_(2)O_(3),Fe_(2)O_(3),NiO_(2),ZrO_(2),La_(2)O_(3)and CeO_(2)) were prepared,characterized and screened to boost the low-temperature combustion of polyethylene waste at 300℃ in air.The mass change,heat release and CO_(x) formation were studied in details and employed to evaluate the combustion rate and efficiency.It was found that CeO_(2)significantly enhanced the combustion rate and efficiency,which was respectively 2 and 7 times that of non-catalytic case.An interesting phenomenon was observed that the catalytic performance of CeO_(2) in polyethylene low-temperature combustion was significantly improved by the 7-day storage in the room environment or water treatment.XPS analysis confirmed the co-existence of Ce^(3+) and Ce^(4+) in CeO_(2),and the 7-day storage and water treatment promoted the amount of Ce^(3+),which facilitated the formation of the oxygen vacancies.That may be the reason why CeO_(2) exhibited excellent catalytic performance in polyethylene low-temperature combustion.

A Generalized Polymer Precursor Ink Design for 3D Printing of Functional Metal Oxides

Three-dimensional-structured metal oxides have myriad applications for optoelectronic devices.Comparing to conventional lithography-based manufacturing methods which face significant challenges for 3D device architectures,additive manufacturing approaches such as direct ink writing offer convenient,on-demand manufacturing of 3D oxides with high resolutions down to sub-micrometer scales.However,the lack of a universal ink design strategy greatly limits the choices of printable oxides.Here,a universal,facile synthetic strategy is developed for direct ink writable polymer precursor inks based on metal-polymer coordination effect.Specifically,polyethyleneimine functionalized by ethylenediaminetetraacetic acid is employed as the polymer matrix for adsorbing targeted metal ions.Next,glucose is introduced as a crosslinker for endowing the polymer precursor inks with a thermosetting property required for 3D printing via the Maillard reaction.For demonstrations,binary(i.e.,ZnO,CuO,In_(2)O_(3),Ga_(2)O_(3),TiO_(2),and Y_(2)O_(3)) and ternary metal oxides(i.e.,BaTiO_(3) and SrTiO_(3)) are printed into 3D architectures with sub-micrometer resolution by extruding the inks through ultrafine nozzles.Upon thermal crosslinking and pyrolysis,the 3D microarchitectures with woodpile geometries exhibit strong light-matter coupling in the mid-infrared region.The design strategy for printable inks opens a new pathway toward 3D-printed optoelectronic devices based on functional oxides.

Homogenous metallic deposition regulated by abundant lithiophilic sites in nickel/cobalt oxides nanoneedle arrays for lithium metal batteries

Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li utilization.Inducing uniform Li plating/stripping is the core of solving these problems.Herein,we design a highly lithiophilic carbon film with an outer sheath of the nanoneedle arrays to induce homogeneous Li plating/stripping.The excellent conductivity and 3D framework of the carbon film not only offer fast charge transport across the entire electrode but also mitigate the volume change of Li metal during cycling.The abundant lithiophilic sites ensure stable Li plating/stripping,thereby inhibiting the Li dendritic growth and"dead"Li formation.The resulting composite anode allows for stable Li stripping/plating under 0.5 mA cm^(-2) with a capacity of 0.5 mA h cm^(-2) for 4000 h and 3 mA cm^(-2) with a capacity of3 mA h cm^(-2) for 1000 h.The Ex-SEM analysis reveals that lithiophilic property is different at the bottom,top,or channel in the structu re,which can regulate a bottom-up uniform Li deposition behavior.Full cells paired with LFP show a stable capacity of 155 mA h g^(-1) under a current density of 0.5C.The pouch cell can keep powering light-emitting diode even under 180°bending,suggesting its good flexibility and great practical applications.

Promotional effect of spherical alumina loading with manganese-based bimetallic oxides on nitric-oxide deep oxidation by ozone

Nitric oxide （NO） deep oxidation to dinitrogen pentoxide （N2O5） by ozone together with wet scrub-bing has become a promising technology for nitrogen-oxide （NOx） removal in industrial boilers. Catalysts were introduced to enhance the N2O5 formation rate with less ozone injection and leakage. A series of monometallic catalysts （manganese, cobalt, cerium, iron, copper, and chromium） as pre-pared by the sol-gel method were tested. The manganese oxides achieved an almost 80% conver-sion efficiency at an ozone （O3）/NO molar ratio of 2.0 in 0.12 s. The crystalline structure and porous parameters were determined. The thermodynamic reaction threshold of NO conversion to N2O5 is oxidation with an O3/NO molar ratio of 1.5. Spherical alumina was selected as the support to achieve the threshold, which was believed to improve the catalytic activity by increasing the surface area and the gas-solid contact time. Based on the manganese oxides, cerium, iron, chromium, cop-per, and cobalt were introduced as promoters. Cerium and iron improved the deep-oxidation effi-ciency compared with manganese/spherical alumina, with less than 50 mg/m3 of outlet NO ＋ nitro-gen oxide, and less than 25 mg/m3 of residual ozone at an O3/NO molar ratio of 1.5. The other three metal oxides inhibited catalytic activity. X-ray diffraction, nitrogen adsorption, hydrogen tempera-ture-programmed reduction, and X-ray photoelectron spectroscopy results indicate that the cata-lytic activity is affected by the synergistic action of NOx oxidation and ozone decomposition.

Advances in Noble Metal-Decorated Metal Oxide Nanomaterials for Chemiresistive Gas Sensors:Overview

Highly sensitive gas sensors with remarkably low detection limits are attractive for diverse practical application fields including real-time environmental monitoring,exhaled breath diagnosis,and food freshness analysis.Among various chemiresistive sensing materials,noble metal-decorated semiconducting metal oxides(SMOs)have currently aroused extensive attention by virtue of the unique electronic and catalytic properties of noble metals.This review highlights the research progress on the designs and applications of different noble metal-decorated SMOs with diverse nanostructures(e.g.,nanoparticles,nanowires,nanorods,nanosheets,nanoflowers,and microspheres)for high-performance gas sensors with higher response,faster response/recovery speed,lower operating temperature,and ultra-low detection limits.The key topics include Pt,Pd,Au,other noble metals(e.g.,Ag,Ru,and Rh.),and bimetals-decorated SMOs containing ZnO,SnO_(2),WO_(3),other SMOs(e.g.,In_(2)O_(3),Fe_(2)O_(3),and CuO),and heterostructured SMOs.In addition to conventional devices,the innovative applications like photo-assisted room temperature gas sensors and mechanically flexible smart wearable devices are also discussed.Moreover,the relevant mechanisms for the sensing performance improvement caused by noble metal decoration,including the electronic sensitization effect and the chemical sensitization effect,have also been summarized in detail.Finally,major challenges and future perspectives towards noble metal-decorated SMOs-based chemiresistive gas sensors are proposed.

Activation of Transition Metal(Fe,Co and Ni)-Oxide Nanoclusters by Nitrogen Defects in Carbon Nanotube for Selective CO_(2) Reduction Reaction

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.

Layered Potassium Titanium Niobate/Reduced Graphene Oxide Nanocomposite as a Potassium‑Ion Battery Anode

With graphite currently leading as the most viable anode for potassium-ion batteries(KIBs),other materials have been left relatively underexamined.Transition metal oxides are among these,with many positive attributes such as synthetic maturity,longterm cycling stability and fast redox kinetics.Therefore,to address this research deficiency we report herein a layered potassium titanium niobate KTiNbO5(KTNO)and its rGO nanocomposite(KTNO/rGO)synthesised via solvothermal methods as a high-performance anode for KIBs.Through effective distribution across the electrically conductive rGO,the electrochemical performance of the KTNO nanoparticles was enhanced.The potassium storage performance of the KTNO/rGO was demonstrated by its first charge capacity of 128.1 mAh g^(−1) and reversible capacity of 97.5 mAh g^(−1) after 500 cycles at 20 mA g^(−1),retaining 76.1%of the initial capacity,with an exceptional rate performance of 54.2 mAh g^(−1)at 1 A g^(−1).Furthermore,to investigate the attributes of KTNO in-situ XRD was performed,indicating a low-strain material.Ex-situ X-ray photoelectron spectra further investigated the mechanism of charge storage,with the titanium showing greater redox reversibility than the niobium.This work suggests this lowstrain nature is a highly advantageous property and well worth regarding KTNO as a promising anode for future high-performance KIBs.