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.

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.

The emerging role of nitric oxide in the synaptic dysfunction of vascular dementia

With an increase in global aging,the number of people affected by cerebrovascular diseases is also increasing,and the incidence of vascular dementia-closely related to cerebrovascular risk-is increasing at an epidemic rate.However,few therapeutic options exist that can markedly improve the cognitive impairment and prognosis of vascular dementia patients.Similarly in Alzheimer’s disease and other neurological disorders,synaptic dysfunction is recognized as the main reason for cognitive decline.Nitric oxide is one of the ubiquitous gaseous cellular messengers involved in multiple physiological and pathological processes of the central nervous system.Recently,nitric oxide has been implicated in regulating synaptic plasticity and plays an important role in the pathogenesis of vascular dementia.This review introduces in detail the emerging role of nitric oxide in physiological and pathological states of vascular dementia and summarizes the diverse effects of nitric oxide on different aspects of synaptic dysfunction,neuroinflammation,oxidative stress,and blood-brain barrier dysfunction that underlie the progress of vascular dementia.Additionally,we propose that targeting the nitric oxide-sGC-cGMP pathway using certain specific approaches may provide a novel therapeutic strategy for vascular dementia.

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.

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.

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.

Effect of Elastic Strains on Adsorption Energies of C,H and O on Transition Metal Oxides

Platinum(Pt)-based noble metal catalysts(PGMs)are the most widely used commercial catalysts,but they have the problems of high cost,low reserves,and susceptibility to small-molecule toxicity.Transition metal oxides(TMOs)are regarded as potential substitutes for PGMs because of their stability in oxidizing environments and excellent catalytic performance.In this study,comprehensive investigation into the influence of elastic strains on the adsorption energies of carbon(C),hydrogen(H)and oxygen(O)on TMOs was conducted.Based on density functional theory(DFT)calculations,these effects in both tetragonal structures(PtO_(2),PdO_(2))and hexagonal structures(ZnO,CdO),along with their respective transition metals were systematically explored.It was identified that the optimal adsorption sites on metal oxides pinpointed the top of oxygen or the top of metal atom,while face-centered cubic(FCC)and hexagonal close-packed(HCP)holes were preferred for the transition metals.Furthermore,under the influence of elastic strains,the results demonstrated significant disparities in the adsorption energies of H and O between oxides and transition metals.Despite these differences,the effect of elastic strains on the adsorption energies of C,H and O on TMOs mirrored those on transition metals:adsorption energies increased under compressive strains,indicating weaker adsorption,and decreased under tension strains,indicating stronger adsorption.This behavior was rationalized based on the d-band model for adsorption atop a metallic atom or the p-band model for adsorption atop an oxygen atom.Consequently,elastic strains present a promising avenue for tailoring the catalytic properties of TMOs.

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.

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.

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.

Recovery of Solid Oxide Fuel CellWaste Heat by Thermoelectric Generators and AlkaliMetal Thermoelectric Converters

A Solid Oxide Fuel Cell(SOFC)is an electrochemical device that converts the chemical energy of a substance into electrical energy through an oxidation-reduction mechanism.The electrochemical reaction of a solid oxide fuel cell(SOFC)generates heat,and this heat can be recovered and put to use in a waste heat recovery system.In addition to preheating the fuel and oxidant,producing steam for industrial use,and heating and cooling enclosed rooms,this waste heat can be used for many more productive uses.The large waste heat produced by SOFCs is a worry that must be managed if they are to be adopted as a viable option in the power generation business.In light of these findings,a novel approach to SOFC waste heat recovery is proposed.The SOFC is combined with a“Thermoelectric Generator and an Alkali Metal Thermoelectric Converter(TG-AMTC)”to transform the excess heat generated by both the SOFC and the TG-AMTC.The proposed TG-AMTC is evaluated using a number of performance indicators including power density,operating temperature,heat recovery rate,exergetic efficiency,energy efficiency,and recovery time.The experimental results state that TG-AMTC has provided an exergetic efficiency,energetic efficiency,and recovery time of 97%,98%,and 23%,respectively.The study proves that the proposed TG-AMTC for SOFC is an efficient method of recovering waste heat.

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.

Ultrasensitive Mechanical Sensor Using Tunable Ordered Array of Metallic and Insulating States in Vanadium Dioxide

Detecting tiny deformations or vibrations, particularly those associated with strains below 1%, is essential in various technological applications. Traditional intrinsic materials, including metals and semiconductors, face challenges in simultaneously achieving initial metallic state and strain-induced insulating state, hindering the development of highly sensitive mechanical sensors. Here we report an ultrasensitive mechanical sensor based on a strain-induced tunable ordered array of metallic and insulating states in the single-crystal bronze-phase vanadium dioxide [VO_(2)(B)] quantum material. It is shown that the initial metallic state in the VO_(2)(B) flake can be tuned to the insulating state by applying a weak uniaxial tensile strain. Such a unique property gives rise to a record-high gauge factor of above 607970, surpassing previous values by an order of magnitude, with excellent linearity and mechanical resilience as well as durability. As a proof-of-concept application, we use our proposed mechanical sensor to demonstrate precise sensing of the micro piece, gentle airflows and water droplets. We attribute the superior performance of the sensor to the strain-induced continuous metal-insulator transition in the single-crystal VO_(2)(B) flake, evidenced by experimental and simulation results. Our findings highlight the potential of exploiting correlated quantum materials for next-generation ultrasensitive flexible mechanical sensors, addressing critical limitations in traditional materials.

Converting an O-vacancy-rich oxide into a multifunctional separator modifier for long-lifespan lithium metal batteries

The lithium metal anode is hailed as the desired "holy grail" for the forthcoming generation of highenergy-density batteries,given its astounding theoretical capacity and low potential.Nonetheless,the formation and growth of dendrites seriously compromise battery life and safety.Herein,an yttriastabilized bismuth oxide(YSB) layer is fabricated on the polypropylene(PP) separator,where YSB reacts with Li anode in-situ in the cell to form a multi-component composite interlayer consisting of Li_(3)Bi,Li_(2)O,and Y_(2)O_(3).The interlayer can function not only as a redistributor to regulate Li^(+) distribution but also as an anion adsorber to increase the Li^(+) transference number from 0.37 to 0.79 for suppressing dendrite nucleation and growth.Consequently,compared with the cell with a baseline separator,those with modified separators exhibit prolonged lifespan in both Li/Li symmetrical cells and Li/Cu half-cells.Notably,the full cells coupled with ultrahigh-loading LiFePO_(4) display an excellent cycling performance of 1700 cycles with a high capacity retention of ~80% at 1 C,exhibiting great potential for practical applications.This work provides a feasible and effective new strategy for separator modification towards building a much-anticipated dendrite-free Li anode and realizing long-lifespan lithium metal batteries.

Metal-to-insulator transitions in 3d-band correlated oxides containing Fe compositions

Metal-to-insulator transitions (MITs),which are achieved in 3d-band correlated transitional metal oxides,trigger abrupt variations in electrical,optical,and/or magnetic properties beyond those of conventional semiconductors.Among such material families,iron(Fe:3d^(6)4s^(2))-containing oxides pique interest owing to their widely tunable MIT properties,which are associated with the various valence states of Fe.Their potential electronic applications also show promise,given the large abundance of Fe on Earth.Representative MIT properties triggered by critical temperature (TMIT) were reported for ReFe_(2)O_(4)(Fe^(2.5+)),ReBaFe_(2)O_(5)(Fe^(2.5+)),Fe_(3)O_(4)(Fe^(2.67+)),Re_(1/3)Sr_(2/3)FeO_(3)(Fe^(3.67+)),Re Cu_(3)Fe_(4)O_(12)(Fe^(3.75+)),and Ca_(1-x)Sr_(x)FeO_(3)(Fe^(4+))(where Re represents rare-earth elements).The common feature of MITs of these Fe-containing oxides is that they are usually accompanied by charge ordering transitions or disproportionation associated with the valence states of Fe.Herein,we review the material family of Fe-containing MIT oxides,their MIT functionalities,and their respective mechanisms.From the perspective of potentially correlated electronic applications,the tunability of the TMITand its resultant resistive change in Fe-containing oxides are summarized and further compared with those of other materials exhibiting MIT functionality.In particular,we highlight the abrupt MIT and wide tunability of TMITof Fe-containing quadruple perovskites,such as Re Cu3Fe4O12.However,their effective material synthesis still needs to be further explored to cater to potential applications.

Heterojunction-engineered carrier transport in elevated-metal metal-oxide thin-film transistors

This study investigates the carrier transport of heterojunction channel in oxide semiconductor thin-film transistor(TFT)using the elevated-metal metal-oxide(EMMO)architecture and indium−zinc oxide(InZnO).The heterojunction band diagram of InZnO bilayer was modified by the cation composition to form the two-dimensional electron gas(2DEG)at the interface quantum well,as verified using a metal−insulator−semiconductor(MIS)device.Although the 2DEG indeed contributes to a higher mobility than the monolayer channel,the competition and cooperation between the gate field and the built-in field strongly affect such mobility-boosting effect,originating from the carrier inelastic collision at the heterojunction interface and the gate field-induced suppression of quantum well.Benefited from the proper energy-band engineering,a high mobility of 84.3 cm2·V^(−1)·s^(−1),a decent threshold voltage(V_(th))of−6.5 V,and a steep subthreshold swing(SS)of 0.29 V/dec were obtained in InZnO-based heterojunction TFT.

Marrying luminescent metal nanoclusters to C_(3)N_(4) for efficient photocatalytic hydrogen peroxide production

Photocatalytic oxygen(O_(2))reduction has been considered a promising method for hydrogen peroxide(H_(2)O_(2))production.However,the poor visible light harvesting and low-efficient separation and generation of charge carriers of conventional photocatalysts strongly limited their photocatalytic H_(2)O_(2) generation performance.Herein,we design a highly efficient photocatalyst in this work by marrying luminescent gold-silver nanoclusters(AuAg NCs)to polyethyleneimine(PEI)modified C_(3)N_(4)(C3N4-PEI).The key design in this work is the utilization of highly luminescent AuAg NCs as photosensitizers to promote the generation and separation of charge carriers of C_(3)N_(4)-PEI,thereby ultimately producing abundant e−for O_(2) reduction under visible light illumination(λ≥400 nm).As a result,the as-designed photocatalyst(C3N4-PEI-AuAg NCs)exhibits excellent photocatalytic activity with an H_(2)O_(2) production capability of 82μM in pure water,which is 3.5 times higher than pristine C_(3)N_(4)(23μM).This interesting design provides a paradigm in developing other high-efficient photocatalysts for visible-light-driven H_(2)O_(2) production.

Development in oxide metallurgy for improving the weldability of high -strength low-alloy steel-Combined deoxidizers and microalloying elements

The mechanisms of oxide metallurgy include inducing the formation of intragranular acicular ferrite(IAF)using micron-sized inclusions and restricting the growth of prior austenite grains(PAGs)by nanosized particles during welding.The chaotically oriented IAF and refined PAGs inhibit crack initiation and propagation in the steel,resulting in high impact toughness.This work summarizes the com-bined effect of deoxidizers and alloying elements,with the aim to provide a new perspective for the research and practice related to im-proving the impact toughness of the heat affected zone(HAZ)during the high heat input welding.Ti complex deoxidation with other strong deoxidants,such as Mg,Ca,Zr,and rare earth metals(REMs),can improve the toughness of the heat-affected zone(HAZ)by re-fining PAGs or increasing IAF contents.However,it is difficult to identify the specific phase responsible for IAF nucleation because ef-fective inclusions formed by complex deoxidation are usually multiphase.Increasing alloying elements,such as C,Si,Al,Nb,or Cr,con-tents can impair HAZ toughness.A high C content typically increases the number of coarse carbides and decreases the potency of IAF formation.Si,Cr,or Al addition leads to the formation of undesirable microstructures.Nb reduces the high-temperature stability of the precipitates.Mo,V,and B can enhance HAZ toughness.Mo-containing precipitates present good thermal stability.VN or V(C,N)is ef-fective in promoting IAF nucleation due to its good coherent crystallographic relationship with ferrite.The formation of the B-depleted zone around the inclusion promotes IAF formation.The interactions between alloying elements are complex,and the effect of adding dif-ferent alloying elements remains to be evaluated.In the future,the interactions between various alloying elements and their effects on ox-ide metallurgy,as well as the calculation of the nucleation effects of effective inclusions using first principles calculations will become the focus of oxide metallurgy.