Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of ...Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of metal in the porphyrins core macrocycle may affect the geometry. The analysis of twists and angles has shown two kinds of distortions: external [T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] and internal [T(N<sup>m</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(N<sup>n</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] with averages of [+6°and –6°] and [–5°and +5°], respectively. In the meso-substituted case, the external and internal twists C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X and N-C<sup>α</sup>-C<sup>meso</sup>-X, respectively are oppositely orientated. Similar effect is observed in meso-unsubstituted of C<sup>β</sup>-C<sup>α</sup>- C<sup>meso</sup>-H and N-C<sup>α</sup>-C<sup>meso</sup>-H. However, the external distortions are more significant than internal. Considering the same order, the limit of distortions is [97°and 132°(–48°)] for external and [91°(–89°) and 52°] for internal. In the two cases, the substituents have opposite directions of distortions. The meso-substituted porphyrins have a high limit of twisting than usubstituted one, depending of the weight of substituents. The average of the bond angular deformations is 168°, almost planar. However, the limit of angular deformation is 94°.展开更多
Metal halides have attracted worldwide attention as exceptional optoelectronic materials.Over the past decade,research on metal halides has yielded remarkable progress,and their color-conversion applications have show...Metal halides have attracted worldwide attention as exceptional optoelectronic materials.Over the past decade,research on metal halides has yielded remarkable progress,and their color-conversion applications have shown considerable promise for commercialization.With the reporting of self-trapped exciton(STE)emission in perovskites,the application of metal halides as broadband emitting materials in the lighting field has gained increas-ing interest.Herein,we provide a comprehensive review of metal halide STE emitters,especially for lighting applications.We begin with highlighting the ideal spectral characteristics and corresponding performance metrics for lighting.This is followed by a systematic summary of the mechanisms,optimization strategies,and recent advances of STE emission in metal halides.Finally,we outline the major challenges and prospective trends for metal halide STE emitters.This review aims to offer valuable insights into metal halide STE emitters and their lighting applications for facilitating the future commercialization.展开更多
Temperature-programmed desorption(TPD)is a fundamental technique in surface science and heterogeneous catalysis for characterizing adsorption behavior,and for extracting key parameters such as adsorption energy.Howeve...Temperature-programmed desorption(TPD)is a fundamental technique in surface science and heterogeneous catalysis for characterizing adsorption behavior,and for extracting key parameters such as adsorption energy.However,the majority of existing TPD data is accessible in the form of published images,which lacks structured and quantitative datasets.This constrains its utility for rigorous quantitative analysis and computational modelling.Using carbon monoxide(CO)which is a widely adopted probe molecule,a curated and standardized dataset of CO-TPD is constructed,encompassing 14 transition-metal single-crystal surfaces,including copper(Cu)and ruthenium(Ru).By systematically extracting numerical data points from published spectra and applying normalization,essential spectral features such as peak shape are fully preserved.The dataset also documents relevant experimental parameters,including heating rates,and was developed using a standardized protocol for data collection and quality control.This resource serves as both a reference library to support the deconvolution of TPD spectra from complex catalysts and an experimental benchmark for calibrating parameters in theoretical models.By providing a reliable and accessible data function,this work advances the microscopic understanding and the rational design of catalyst active centers.展开更多
39 soil samples surrounding a lead-zinc mining area in Guangxi were collected,and the contents of Pb,Hg,Cd,Cr,As,Cu,Zn,and Ni were determined to investigate the pollution characteristics and sources of heavy metals.Ar...39 soil samples surrounding a lead-zinc mining area in Guangxi were collected,and the contents of Pb,Hg,Cd,Cr,As,Cu,Zn,and Ni were determined to investigate the pollution characteristics and sources of heavy metals.ArcGIS inverse distance weight difference method was used to analyze the characteristics of pollution distribution,and single-factor pollution index,Nemerow comprehensive pollution index,ground accumulation index,and potential ecological risk index were selected to evaluate the characteristics of heavy metal pollution.Based on correlation analysis,the absolute principal component-multiple linear regression(APCS-MLR)and positive definite matrix factorization(PMF)models were used to analyze the sources of soil heavy metals.The results showed that the average concentrations of all eight heavy metals exceeded both national and Guangxi soil background values.Hg,Cd,and Zn exhibited high variation(greater than 0.5),indicating significant external disturbances,and their spatial distribution was closely related to mining activity locations.The single-factor pollution index evaluation indicated varying degrees of pollution risk for Cd,Zn,and As,with Cd and Zn being the most severe pollutants,as 69.23%and 30.77%of the samples fell into the moderate pollution or higher category.The geoaccumulation index analysis ranked the mean pollution levels of the eight elements as follows:Zn>Cd>Ni>Pb>Cu>Cr>Hg>As,with Cd and Zn showing the most severe contamination,and 51.28%of the samples exhibiting moderate or higher pollution levels.The Nemerow comprehensive pollution index evaluation showed that 74.35%of soil samples were classified as moderate to heavy pollution.The potential ecological risk index assessment indicated significant ecological risks posed by Cd and Zn,with 82.05%and 5.12%of the samples classified as causing strong to extreme ecological risks,respectively.The source apportionment analysis revealed minor differences between the two models.The APCS-MLR model identified three pollution sources and their contribution rates:anthropogenic mining sources(31.13%),parent material sources(40.38%),and unidentified sources(28.49%).The PMF model identified three pollution sources with contribution rates of anthropogenic mining sources(26.10%),parent material sources(46.96%),and a combined traffic and agricultural source(26.61%).Pb,Hg,Cd,and Zn mainly originated from mining activities;Cr,As,and Ni were primarily derived from the parent material,while Cu was predominantly attributed to traffic and agricultural sources.These findings provide a scientific basis for the prevention and control of heavy metal pollution in mining areas.展开更多
Chemical looping methane steam reforming(CL-MSR)has garnered significant attention owing to its ability to sequentially produce syngas with high selectivity and high-purity hydrogen through redox cycling.To overcome t...Chemical looping methane steam reforming(CL-MSR)has garnered significant attention owing to its ability to sequentially produce syngas with high selectivity and high-purity hydrogen through redox cycling.To overcome the limitations of single ironbased oxygen carriers,including poor cycling stability,low reactivity and susceptibility to sintering,this study employed a dipcoating method to modify Fe_(2)O_(3)/Al_(2)O_(3)oxygen carriers by incorporating three distinct metal additives:Cu,La and Ce.The composite oxygen carriers were systematically characterized and evaluated under redox conditions to investigate the structure-activity relationships between the physicochemical properties,reactivity,and hydrogen production performance.Results revealed that the spinel-phase CuFe_(2)O_(4)exhibited higher reactivity than the perovskite-phase LaFeO_(3)and CeO_(2),promoting the deeper reduction of Fe_(2)O_(3).Fe58Cu2Al exhibited an oxygen storage capacity as high as 6.5 mmol/g.During the CH4 reaction stage,Fe58Cu2Al achieved the highest oxygen loss of 12.1 g/100 g oxygen carrier,accompanied by a syngas yield of 5.15 mmol/g-1.33 times and 1.59 times greater than that of Fe60Al.In the hydrogen production stage,the 2%Cu-modified oxygen carrier demonstrated optimal performance,yielding 5.13 mmol/g of hydrogen,which was 1.51 times that of the pristine sample.Even after ten cycles,the H_(2)yield remained at 3.61 mmol/g,surpassing the single-cycle output of the pristine sample and the H2 purity consistently exceeded 98%.展开更多
Refractory metals,including tungsten(W),tantalum(Ta),molybdenum(Mo),and niobium(Nb),play a vital role in industries,such as nuclear energy and aerospace,owing to their exceptional melting temperatures,thermal durabili...Refractory metals,including tungsten(W),tantalum(Ta),molybdenum(Mo),and niobium(Nb),play a vital role in industries,such as nuclear energy and aerospace,owing to their exceptional melting temperatures,thermal durability,and corrosion resistance.These metals have body-centered cubic crystal structure,characterized by limited slip systems and impeded dislocation motion,resulting in significant low-temperature brittleness,which poses challenges for the conventional processing.Additive manufacturing technique provides an innovative approach,enabling the production of intricate parts without molds,which significantly improves the efficiency of material usage.This review provides a comprehensive overview of the advancements in additive manufacturing techniques for the production of refractory metals,such as W,Ta,Mo,and Nb,particularly the laser powder bed fusion.In this review,the influence mechanisms of key process parameters(laser power,scan strategy,and powder characteristics)on the evolution of material microstructure,the formation of metallurgical defects,and mechanical properties were discussed.Generally,optimizing powder characteristics,such as sphericity,implementing substrate preheating,and formulating alloying strategies can significantly improve the densification and crack resistance of manufactured parts.Meanwhile,strictly controlling the oxygen impurity content and optimizing the energy density input are also the key factors to achieve the simultaneous improvement in strength and ductility of refractory metals.Although additive manufacturing technique provides an innovative solution for processing refractory metals,critical issues,such as residual stress control,microstructure and performance anisotropy,and process stability,still need to be addressed.This review not only provides a theoretical basis for the additive manufacturing of high-performance refractory metals,but also proposes forward-looking directions for their industrial application.展开更多
Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materi...Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materials,they have gained essential applications in the aerospace field and have excellent prospects for application in frontier military fields,such as protecting hot-end components of hypersonic aircraft.This research reviewed the latest research progress of platinum group metal coatings with hightemperature oxidation resistance,including coating preparation techniques,oxidation failure,and alloying modification.The leading preparation techniques of current platinum group metal coatings were discussed,as well as the advantages and disadvantages of various existing preparation techniques.Besides,the intrinsic properties,failure forms,and failure mechanisms of coatings of single platinum group metal in high-temperature oxygen-containing environments were analyzed.On this basis,the necessity,main methods,and main achievements of alloying modification of platinum group metals were summarized.Finally,the future development of platinum group coatings with high-temperature oxidation resistance was discussed and prospected.展开更多
T he residual stray magnetic fields present in ferromagnetic casting slabs were investigated in this work,which result from the magnetic fields generated during the steel casting process.Existing optical detection met...T he residual stray magnetic fields present in ferromagnetic casting slabs were investigated in this work,which result from the magnetic fields generated during the steel casting process.Existing optical detection methods face challenges owing to surface oxide scales,and conventional high-precision magnetic sensors are ineffective at high temperatures.To overcome these limitations,a small coil sensor was employed to measure the residual magnetism strength in oscillation traces,using metal magnetic memory and electromagnetic induction methods,which can carry out detection without an external excitation source.Using this technology,the proposed scheme successfully detects defects at high tempe-ratures(up to 670℃)without a cooling device.The key findings include the ability to detect both surface and near-surface defects,such as cracks and oscillation marks,with an enhanced signal-to-noise ratio(SNR)of 7.2 dB after signal processing.The method’s practicality was validated in a steel mill environment,where testing on casting slabs effectively detected defects,providing a foundation for improving industrial quality control.The proposed detection scheme offers a significant advancement in nondestructive testing(NDT)for high-temperature applications,contributing to more efficient and accurate monitoring of ferromagnetic material integrity.展开更多
Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellen...Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellent catalytic activity,a remarkable adsorption capacity,and different interfacial physicochemical functionalities.Surface-modified biochars have found wide applications in energy storage,environmental remediation,and catalysis.However,achieving precise and controllable modification of their active sites remains a challenge.Recent advances and future prospects for controlling their surface morphology,defect engineering,and surface coating strategies,with particular attention to their means of fabrication,are reviewed.展开更多
Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport ...Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge‑discharge cycles.Electrochemical characterization under a three‑electrode system revealed exceptional rate capability:Mn@PN delivered an ultrahigh specific capacitance of 10318 F·g^(-1) at a low current density of 3 A·g^(-1) and retained 9415 F·g^(-1)(91.2%retention compared to the value at 3 A·g^(-1))even at an ultrahigh current density of 50 A·g^(-1).Moreover,the material exhibited 97.4%capacitance retention after 9000 cycles at 30 A·g^(-1),corresponding with a low capacitance decay rate of 0.003‰per cycle,significantly outperforming conventional conductive polymers like polyaniline(PANI).An asymmetric supercapacitor assembled with Mn@PN as the positive electrode(Mn@PN||AC)achieved an energy density of 328 Wh·kg^(-1) at 15 A·g^(-1) and retained 80.7%of its initial specific capacitance after 4000 cycles at 20 A·g^(-1).展开更多
The Ni/SBA-15 catalysts were synthesized using the in situ method and the influence of crystallization temperature on nickel utilization efficiency-a critical factor in mesoporous material design-was systematically in...The Ni/SBA-15 catalysts were synthesized using the in situ method and the influence of crystallization temperature on nickel utilization efficiency-a critical factor in mesoporous material design-was systematically investigated.The structural characteristics and nickel anchoring capacity were analyzed using XRD,BET,FT-IR,H2-TPR,and ICP-OES.The results demonstrated that the crystallization temperature significantly affected the framework order of SBA-15 and the surface anchoring efficiency of Ni ions.The nickel utilization efficiency increased from 8.4%at 80℃to 60.49%at 140℃,but then decreased to 47.25%at 160℃,indicating an optimal crystallization temperature window.This provides crucial guidance for tailoring high-performance metal-doped molecular sieves.The optimal catalyst exhibited excellent performance in the hydrogenation of 1,4-butynediol(BYD):the BYD conversion reached 97.25%with 88.99%selectivity of 1,4-butenediol(BED)within 5 h,and reached 99.73%with 87.34%selectivity of 1,4-butanediol(BDO)after 20 h reaction.These results revealed the critical role of crystallization temperature in metal utilization and provided theoretical support for designing highly active molecular sieve catalysts.展开更多
Transition metal-catalyzed C—C coupling reactions are a core strategy for the construction of carbon-carbon bonds in organic synthesis.Their development has not only promoted the synthesis of drugs,materials,and natu...Transition metal-catalyzed C—C coupling reactions are a core strategy for the construction of carbon-carbon bonds in organic synthesis.Their development has not only promoted the synthesis of drugs,materials,and natural products,but also promoted the development of new synthetic methods,and has also made breakthroughs in mechanism innovation and catalyst design.On this basis,a copper-catalyzed radical reaction between ketones is reported,enabling the synthesis of 2-carbonyl-1,4-diones.The method exhibits excellent applicability to multiple structural types of ketones,including aliphatic ketones with diverse substituents,aromatic ketones,and various simple ketones not limited to acetone,with wide applications,easy implementation,low catalyst toxicity,and low cost,cost-effective,and the product is easy to separate and purify.展开更多
In this study,using 3,5‑di(3′,5′‑dicarboxylphenyl)‑1H‑1,2,4‑triazole(H4L)as ligands,a gadolinia‑based organic framework complex{[GdNa(L)(H_(2)O)3]·2H_(2)O}_(n)(Gd‑Na‑MOF)was successfully designed and synthesize...In this study,using 3,5‑di(3′,5′‑dicarboxylphenyl)‑1H‑1,2,4‑triazole(H4L)as ligands,a gadolinia‑based organic framework complex{[GdNa(L)(H_(2)O)3]·2H_(2)O}_(n)(Gd‑Na‑MOF)was successfully designed and synthesized by hydrothermal method.The structure and properties were systematically characterized and tested by techniques such as single‑crystal X‑ray diffraction,powder X‑ray diffraction,thermogravimetric analysis,infrared spectroscopy,and fluorescence spectroscopy.The results indicate that this complex has a unique 3D structure,excellent thermal stability,and outstanding luminescent performance.Based on its luminescent properties,a polymer‑embedding method was employed to fabricate the Gd‑Na‑MOF into a flexible,washable composite fluorescent film,Gd‑Na‑MOF@PMMA/BMA(PMMA=polymethyl methacrylate,BMA=butyl methacrylate).This fluorescent film exhibited highly sensitive recognition capability for tyramine,with a low detection limit of 1.66μmol·L^(-1).It was used for the detection of tyramine in bananas,with a recovery rate of 96.92%‑100.26%.CCDC:2466949.展开更多
《中国有色金属学报》和《Transactions of Nonferrous Metals Society of China》(《中国有色金属学报(英文版)》)是中国有色金属学会主办、科学出版社出版的学术期刊。创刊于1991年,主要报道我国有色金属材料、冶金、选矿和化学化工...《中国有色金属学报》和《Transactions of Nonferrous Metals Society of China》(《中国有色金属学报(英文版)》)是中国有色金属学会主办、科学出版社出版的学术期刊。创刊于1991年,主要报道我国有色金属材料、冶金、选矿和化学化工领域的新理论、新技术和新方法。《中国有色金属学报》为月刊,80元/期,全年订价960元。邮发代号:42−218。展开更多
Lithium metal batteries(LMBs)are promising candidates for next-generation high-energy-density storage devices.However,an unstable lithium metal anode poses significant issues that critically compromise battery safety ...Lithium metal batteries(LMBs)are promising candidates for next-generation high-energy-density storage devices.However,an unstable lithium metal anode poses significant issues that critically compromise battery safety and cycle life,including lithium dendrite formation,solid electrolyte interphase degradation,dead lithium accumulation,and substantial volume fluctuations during cycling.These problems can be addressed by regulating lithium deposition and suppressing side reactions through the modification of copper current collectors using three classes of materials:metal and metal oxide,carbon,and polymer materials.This review comprehensively examines recent advances in the application of these materials as current collector coatings.Particularly,their distinct roles in the lithium deposition process are analyzed to understand how they mitigate the issues associated with the lithium metal anode.Furthermore,their inherent limitations are considered to inform future research directions.While each class of materials offers specific advantages,multifunctionality is required to effectively regulate lithium deposition.In prospect,a novel composite copper current collector design that integrates the merits of the aforementioned advanced materials is proposed.The insights from this review provide valuable guidance for the rational design of modified copper current collectors,which would significantly improve the safety and cycle life of LMBs and advance their commercialization.展开更多
Metals,indispensable since the Bronze Age,remain pivotal in modern technologies due to their exceptional properties and versatility.Beyond traditional machining,advanced nano/micro-machining techniques enable the fabr...Metals,indispensable since the Bronze Age,remain pivotal in modern technologies due to their exceptional properties and versatility.Beyond traditional machining,advanced nano/micro-machining techniques enable the fabrication of metallic nano/micro structures with high precision in shape,size,and pattern.These structures endow flexible electrodes with outstanding electrical,mechanical,optical,and electrochemical performance,enabling growing applications in flexible optoelectronics,epidermal electronics,energy harvesting,and biochemical sensing.This review provides a comprehensive overview of the fabrication strategies for flexible electrodes made from metal meshes,metal nanowires,and liquid metals.The current advancements,existing challenges,and emerging technologies are systematically discussed.Furthermore,the progression toward ultra-thin,soft epidermal electrodes is explored,with an emphasis on novel in situ and transfer fabrication methods.We examine the underlying mechanisms,performance indicators,and their integration for on-skin applications,including bioelectric sensing,electrical stimulation,and energy harvesting.Finally,we highlight the remaining challenges in performance improvement and industrialization of flexible and epidermal electrodes,along with future opportunities for integrating multimodal systems and leveraging artificial intelligence to enhance their functionalities.展开更多
Neurodegenerative diseases,which mainly include Alzheimer’s disease,Parkinson’s disease,amyotrophic lateral sclerosis,Wilson’s disease,and Huntington’s disease,are a group of disorders characterized by loss of neu...Neurodegenerative diseases,which mainly include Alzheimer’s disease,Parkinson’s disease,amyotrophic lateral sclerosis,Wilson’s disease,and Huntington’s disease,are a group of disorders characterized by loss of neurons in the brain and spinal cord.However,the underlying pathogenetic mechanisms of these disorders remain unclear.The metal ion hypothesis is considered a possible cause of a variety of neurodegenerative diseases.This hypothesis posits that the homeostatic imbalance of metal ions leads to oxidative stress,neuroinflammation,excessive aggregation of pathological proteins,and other serious consequences in neurons.The powerful endogenous metal ion chelator metallothionein plays an important role in regulating metal ion homeostasis to alleviate neurodegenerative diseases.This article provides an overview of the pathogenesis of neurodegenerative diseases in relation to metal ions such as copper,iron,and zinc and the contribution of metallothionein to the regulation of metal ion homeostasis.The review focuses on the role of metal ions in the course of neurodegenerative diseases and the molecular mechanisms through which endogenous metallothionein ameliorates metal ion overload to alleviate neurodegenerative diseases.A thorough understanding of these molecular mechanisms can provide a theoretical foundation for the development of new therapeutic strategies,with the aim of more effectively treating these devastating diseases in the future.展开更多
The Kagome metal CsV3Sb5 transitions from a weakly correlated state to a strongly correlated state upon Cr substitution;however,the mechanism driving this enhancement remains an open question.Here,we employed a combin...The Kagome metal CsV3Sb5 transitions from a weakly correlated state to a strongly correlated state upon Cr substitution;however,the mechanism driving this enhancement remains an open question.Here,we employed a combination of density functional theory and dynamical mean-field theory(DFT+DMFT)to systematically investigate the evolution of electronic correlations in the CsV_(3−x)Cr_(x)Sb_(5)(x=0,1,and 3)series.Our calculations revealed that Cr doping drives the system into a strongly correlated Hund’s metal phase,which is characterized by significant and orbital-dependent enhancements in the quasiparticle effective masses and electronic scattering rates.We trace the origin of this transition to the doping-induced shift from low-to high-spin atomic configurations.This preference for high-spin states,which is promoted by near-half-filling of the Cr-d orbitals,induces a pronounced orbital blocking effect that strengthens the correlations.Our findings establish that Hund’s coupling is the decisive factor governing the rich correlation physics in the CsV_(3−x)Cr_(x)Sb_(5) family,providing a tunable platform for exploring Hund’s metallicity.展开更多
Lithium metal anodes are promising for next-generation high-energy batteries,but their practical application is limited by safety issues arising from uncontrolled Li metal growth.To address these challenges,we report ...Lithium metal anodes are promising for next-generation high-energy batteries,but their practical application is limited by safety issues arising from uncontrolled Li metal growth.To address these challenges,we report a scalable approach to fabricate flexible,free-standing 3D carbon textiles derived from low-cost cellulose textiles,uniformly decorated with cobalt particles(Co@c-Textile).The work function difference between cobalt particles and carbon induces a redistribution of surface charge,enabling the synergistic combination of cobalt and defective carbon to enhance lithiophilicity and promote uniform Li growth through accelerate surface diffusion.Detailed analyses further reveal that lithium preferentially plates not directly on the cobalt particles,but on the adjacent carbon regions,eventually encapsulating the cobalt and growing uniformly across the carbon surface.As a result,the Co@c-Textile@Li anode exhibits prolonged and stable cycling over 700 h in symmetric cells,along with improved Li+transport kinetics.Furthermore,in full-cells with Li Fe PO_(4)(LFP)cathodes,it delivers over 90%capacity retention at both1C and 4C,and also demonstrates excellent stability under high-voltage conditions with Ni-rich cathodes.These findings clarify the role of transition metal/carbon composites in directing uniform Li plating and provide a viable strategy for designing advanced carbon-hosted Li metal anodes.展开更多
文摘Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of metal in the porphyrins core macrocycle may affect the geometry. The analysis of twists and angles has shown two kinds of distortions: external [T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] and internal [T(N<sup>m</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(N<sup>n</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] with averages of [+6°and –6°] and [–5°and +5°], respectively. In the meso-substituted case, the external and internal twists C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X and N-C<sup>α</sup>-C<sup>meso</sup>-X, respectively are oppositely orientated. Similar effect is observed in meso-unsubstituted of C<sup>β</sup>-C<sup>α</sup>- C<sup>meso</sup>-H and N-C<sup>α</sup>-C<sup>meso</sup>-H. However, the external distortions are more significant than internal. Considering the same order, the limit of distortions is [97°and 132°(–48°)] for external and [91°(–89°) and 52°] for internal. In the two cases, the substituents have opposite directions of distortions. The meso-substituted porphyrins have a high limit of twisting than usubstituted one, depending of the weight of substituents. The average of the bond angular deformations is 168°, almost planar. However, the limit of angular deformation is 94°.
文摘Metal halides have attracted worldwide attention as exceptional optoelectronic materials.Over the past decade,research on metal halides has yielded remarkable progress,and their color-conversion applications have shown considerable promise for commercialization.With the reporting of self-trapped exciton(STE)emission in perovskites,the application of metal halides as broadband emitting materials in the lighting field has gained increas-ing interest.Herein,we provide a comprehensive review of metal halide STE emitters,especially for lighting applications.We begin with highlighting the ideal spectral characteristics and corresponding performance metrics for lighting.This is followed by a systematic summary of the mechanisms,optimization strategies,and recent advances of STE emission in metal halides.Finally,we outline the major challenges and prospective trends for metal halide STE emitters.This review aims to offer valuable insights into metal halide STE emitters and their lighting applications for facilitating the future commercialization.
基金Supported by the Robotic AI-Scientist Platform of Chinese Academy of SciencesNational Natural Science Foundation of China(22372185)+2 种基金Youth Talent Development Program of SKLCC(2025BWZ009)Natural Science Foundation of Shanxi Province(202203021221219)Research on the Construction of Scientific and Technological Innovation Think Tank of Shanxi Association for Science and Technology(KXKT202542)。
文摘Temperature-programmed desorption(TPD)is a fundamental technique in surface science and heterogeneous catalysis for characterizing adsorption behavior,and for extracting key parameters such as adsorption energy.However,the majority of existing TPD data is accessible in the form of published images,which lacks structured and quantitative datasets.This constrains its utility for rigorous quantitative analysis and computational modelling.Using carbon monoxide(CO)which is a widely adopted probe molecule,a curated and standardized dataset of CO-TPD is constructed,encompassing 14 transition-metal single-crystal surfaces,including copper(Cu)and ruthenium(Ru).By systematically extracting numerical data points from published spectra and applying normalization,essential spectral features such as peak shape are fully preserved.The dataset also documents relevant experimental parameters,including heating rates,and was developed using a standardized protocol for data collection and quality control.This resource serves as both a reference library to support the deconvolution of TPD spectra from complex catalysts and an experimental benchmark for calibrating parameters in theoretical models.By providing a reliable and accessible data function,this work advances the microscopic understanding and the rational design of catalyst active centers.
文摘39 soil samples surrounding a lead-zinc mining area in Guangxi were collected,and the contents of Pb,Hg,Cd,Cr,As,Cu,Zn,and Ni were determined to investigate the pollution characteristics and sources of heavy metals.ArcGIS inverse distance weight difference method was used to analyze the characteristics of pollution distribution,and single-factor pollution index,Nemerow comprehensive pollution index,ground accumulation index,and potential ecological risk index were selected to evaluate the characteristics of heavy metal pollution.Based on correlation analysis,the absolute principal component-multiple linear regression(APCS-MLR)and positive definite matrix factorization(PMF)models were used to analyze the sources of soil heavy metals.The results showed that the average concentrations of all eight heavy metals exceeded both national and Guangxi soil background values.Hg,Cd,and Zn exhibited high variation(greater than 0.5),indicating significant external disturbances,and their spatial distribution was closely related to mining activity locations.The single-factor pollution index evaluation indicated varying degrees of pollution risk for Cd,Zn,and As,with Cd and Zn being the most severe pollutants,as 69.23%and 30.77%of the samples fell into the moderate pollution or higher category.The geoaccumulation index analysis ranked the mean pollution levels of the eight elements as follows:Zn>Cd>Ni>Pb>Cu>Cr>Hg>As,with Cd and Zn showing the most severe contamination,and 51.28%of the samples exhibiting moderate or higher pollution levels.The Nemerow comprehensive pollution index evaluation showed that 74.35%of soil samples were classified as moderate to heavy pollution.The potential ecological risk index assessment indicated significant ecological risks posed by Cd and Zn,with 82.05%and 5.12%of the samples classified as causing strong to extreme ecological risks,respectively.The source apportionment analysis revealed minor differences between the two models.The APCS-MLR model identified three pollution sources and their contribution rates:anthropogenic mining sources(31.13%),parent material sources(40.38%),and unidentified sources(28.49%).The PMF model identified three pollution sources with contribution rates of anthropogenic mining sources(26.10%),parent material sources(46.96%),and a combined traffic and agricultural source(26.61%).Pb,Hg,Cd,and Zn mainly originated from mining activities;Cr,As,and Ni were primarily derived from the parent material,while Cu was predominantly attributed to traffic and agricultural sources.These findings provide a scientific basis for the prevention and control of heavy metal pollution in mining areas.
基金Supported by the National Natural Science Foundation of China(52266008,52464057)Applied Basic Research Program of Yunnan Province(202301AT070067)the Yunnan Revitalization Talent Support Program Young Talent Project(XDYC-QNRC-2022-0060)。
文摘Chemical looping methane steam reforming(CL-MSR)has garnered significant attention owing to its ability to sequentially produce syngas with high selectivity and high-purity hydrogen through redox cycling.To overcome the limitations of single ironbased oxygen carriers,including poor cycling stability,low reactivity and susceptibility to sintering,this study employed a dipcoating method to modify Fe_(2)O_(3)/Al_(2)O_(3)oxygen carriers by incorporating three distinct metal additives:Cu,La and Ce.The composite oxygen carriers were systematically characterized and evaluated under redox conditions to investigate the structure-activity relationships between the physicochemical properties,reactivity,and hydrogen production performance.Results revealed that the spinel-phase CuFe_(2)O_(4)exhibited higher reactivity than the perovskite-phase LaFeO_(3)and CeO_(2),promoting the deeper reduction of Fe_(2)O_(3).Fe58Cu2Al exhibited an oxygen storage capacity as high as 6.5 mmol/g.During the CH4 reaction stage,Fe58Cu2Al achieved the highest oxygen loss of 12.1 g/100 g oxygen carrier,accompanied by a syngas yield of 5.15 mmol/g-1.33 times and 1.59 times greater than that of Fe60Al.In the hydrogen production stage,the 2%Cu-modified oxygen carrier demonstrated optimal performance,yielding 5.13 mmol/g of hydrogen,which was 1.51 times that of the pristine sample.Even after ten cycles,the H_(2)yield remained at 3.61 mmol/g,surpassing the single-cycle output of the pristine sample and the H2 purity consistently exceeded 98%.
基金National MCF Energy R&D Program(2024YFE03260300)。
文摘Refractory metals,including tungsten(W),tantalum(Ta),molybdenum(Mo),and niobium(Nb),play a vital role in industries,such as nuclear energy and aerospace,owing to their exceptional melting temperatures,thermal durability,and corrosion resistance.These metals have body-centered cubic crystal structure,characterized by limited slip systems and impeded dislocation motion,resulting in significant low-temperature brittleness,which poses challenges for the conventional processing.Additive manufacturing technique provides an innovative approach,enabling the production of intricate parts without molds,which significantly improves the efficiency of material usage.This review provides a comprehensive overview of the advancements in additive manufacturing techniques for the production of refractory metals,such as W,Ta,Mo,and Nb,particularly the laser powder bed fusion.In this review,the influence mechanisms of key process parameters(laser power,scan strategy,and powder characteristics)on the evolution of material microstructure,the formation of metallurgical defects,and mechanical properties were discussed.Generally,optimizing powder characteristics,such as sphericity,implementing substrate preheating,and formulating alloying strategies can significantly improve the densification and crack resistance of manufactured parts.Meanwhile,strictly controlling the oxygen impurity content and optimizing the energy density input are also the key factors to achieve the simultaneous improvement in strength and ductility of refractory metals.Although additive manufacturing technique provides an innovative solution for processing refractory metals,critical issues,such as residual stress control,microstructure and performance anisotropy,and process stability,still need to be addressed.This review not only provides a theoretical basis for the additive manufacturing of high-performance refractory metals,but also proposes forward-looking directions for their industrial application.
文摘Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materials,they have gained essential applications in the aerospace field and have excellent prospects for application in frontier military fields,such as protecting hot-end components of hypersonic aircraft.This research reviewed the latest research progress of platinum group metal coatings with hightemperature oxidation resistance,including coating preparation techniques,oxidation failure,and alloying modification.The leading preparation techniques of current platinum group metal coatings were discussed,as well as the advantages and disadvantages of various existing preparation techniques.Besides,the intrinsic properties,failure forms,and failure mechanisms of coatings of single platinum group metal in high-temperature oxygen-containing environments were analyzed.On this basis,the necessity,main methods,and main achievements of alloying modification of platinum group metals were summarized.Finally,the future development of platinum group coatings with high-temperature oxidation resistance was discussed and prospected.
文摘T he residual stray magnetic fields present in ferromagnetic casting slabs were investigated in this work,which result from the magnetic fields generated during the steel casting process.Existing optical detection methods face challenges owing to surface oxide scales,and conventional high-precision magnetic sensors are ineffective at high temperatures.To overcome these limitations,a small coil sensor was employed to measure the residual magnetism strength in oscillation traces,using metal magnetic memory and electromagnetic induction methods,which can carry out detection without an external excitation source.Using this technology,the proposed scheme successfully detects defects at high tempe-ratures(up to 670℃)without a cooling device.The key findings include the ability to detect both surface and near-surface defects,such as cracks and oscillation marks,with an enhanced signal-to-noise ratio(SNR)of 7.2 dB after signal processing.The method’s practicality was validated in a steel mill environment,where testing on casting slabs effectively detected defects,providing a foundation for improving industrial quality control.The proposed detection scheme offers a significant advancement in nondestructive testing(NDT)for high-temperature applications,contributing to more efficient and accurate monitoring of ferromagnetic material integrity.
文摘Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellent catalytic activity,a remarkable adsorption capacity,and different interfacial physicochemical functionalities.Surface-modified biochars have found wide applications in energy storage,environmental remediation,and catalysis.However,achieving precise and controllable modification of their active sites remains a challenge.Recent advances and future prospects for controlling their surface morphology,defect engineering,and surface coating strategies,with particular attention to their means of fabrication,are reviewed.
文摘Herein,manganese(Mn)‑doped poly(1,5‑diaminonaphthalene)(PN)electrode material(Mn@PN)was synthesized via chemical oxidative polymerization.The material′s distinctive vesicular architecture enables rapid ion transport while maintaining the structural stability of the electrode under continuous charge‑discharge cycles.Electrochemical characterization under a three‑electrode system revealed exceptional rate capability:Mn@PN delivered an ultrahigh specific capacitance of 10318 F·g^(-1) at a low current density of 3 A·g^(-1) and retained 9415 F·g^(-1)(91.2%retention compared to the value at 3 A·g^(-1))even at an ultrahigh current density of 50 A·g^(-1).Moreover,the material exhibited 97.4%capacitance retention after 9000 cycles at 30 A·g^(-1),corresponding with a low capacitance decay rate of 0.003‰per cycle,significantly outperforming conventional conductive polymers like polyaniline(PANI).An asymmetric supercapacitor assembled with Mn@PN as the positive electrode(Mn@PN||AC)achieved an energy density of 328 Wh·kg^(-1) at 15 A·g^(-1) and retained 80.7%of its initial specific capacitance after 4000 cycles at 20 A·g^(-1).
文摘The Ni/SBA-15 catalysts were synthesized using the in situ method and the influence of crystallization temperature on nickel utilization efficiency-a critical factor in mesoporous material design-was systematically investigated.The structural characteristics and nickel anchoring capacity were analyzed using XRD,BET,FT-IR,H2-TPR,and ICP-OES.The results demonstrated that the crystallization temperature significantly affected the framework order of SBA-15 and the surface anchoring efficiency of Ni ions.The nickel utilization efficiency increased from 8.4%at 80℃to 60.49%at 140℃,but then decreased to 47.25%at 160℃,indicating an optimal crystallization temperature window.This provides crucial guidance for tailoring high-performance metal-doped molecular sieves.The optimal catalyst exhibited excellent performance in the hydrogenation of 1,4-butynediol(BYD):the BYD conversion reached 97.25%with 88.99%selectivity of 1,4-butenediol(BED)within 5 h,and reached 99.73%with 87.34%selectivity of 1,4-butanediol(BDO)after 20 h reaction.These results revealed the critical role of crystallization temperature in metal utilization and provided theoretical support for designing highly active molecular sieve catalysts.
基金Project supported by the Basic Research Support Program for Outstanding Young Teachers in Provincial Undergraduate Colleges and Universities in Heilongjiang Province(No.YQJH2024096)the Heilongjiang Province Natural Joint Guidance Cultivation Project(No.PL2024H198)。
文摘Transition metal-catalyzed C—C coupling reactions are a core strategy for the construction of carbon-carbon bonds in organic synthesis.Their development has not only promoted the synthesis of drugs,materials,and natural products,but also promoted the development of new synthetic methods,and has also made breakthroughs in mechanism innovation and catalyst design.On this basis,a copper-catalyzed radical reaction between ketones is reported,enabling the synthesis of 2-carbonyl-1,4-diones.The method exhibits excellent applicability to multiple structural types of ketones,including aliphatic ketones with diverse substituents,aromatic ketones,and various simple ketones not limited to acetone,with wide applications,easy implementation,low catalyst toxicity,and low cost,cost-effective,and the product is easy to separate and purify.
文摘In this study,using 3,5‑di(3′,5′‑dicarboxylphenyl)‑1H‑1,2,4‑triazole(H4L)as ligands,a gadolinia‑based organic framework complex{[GdNa(L)(H_(2)O)3]·2H_(2)O}_(n)(Gd‑Na‑MOF)was successfully designed and synthesized by hydrothermal method.The structure and properties were systematically characterized and tested by techniques such as single‑crystal X‑ray diffraction,powder X‑ray diffraction,thermogravimetric analysis,infrared spectroscopy,and fluorescence spectroscopy.The results indicate that this complex has a unique 3D structure,excellent thermal stability,and outstanding luminescent performance.Based on its luminescent properties,a polymer‑embedding method was employed to fabricate the Gd‑Na‑MOF into a flexible,washable composite fluorescent film,Gd‑Na‑MOF@PMMA/BMA(PMMA=polymethyl methacrylate,BMA=butyl methacrylate).This fluorescent film exhibited highly sensitive recognition capability for tyramine,with a low detection limit of 1.66μmol·L^(-1).It was used for the detection of tyramine in bananas,with a recovery rate of 96.92%‑100.26%.CCDC:2466949.
文摘《中国有色金属学报》和《Transactions of Nonferrous Metals Society of China》(《中国有色金属学报(英文版)》)是中国有色金属学会主办、科学出版社出版的学术期刊。创刊于1991年,主要报道我国有色金属材料、冶金、选矿和化学化工领域的新理论、新技术和新方法。《中国有色金属学报》为月刊,80元/期,全年订价960元。邮发代号:42−218。
基金supported by the National Natural Science Foundation of China(grant numbers 52071225,22179143,and 22002176)the European Union’s Horizon Europe research and innovation program Electron Beam Emergent Additive Manufacturing(EBEAM)(grant number 101087143)+2 种基金a Norway Grant through the National Science Centre(project number 2019/34/H/ST8/00547)the National Key R&D Program of China(grant number 2021YFB3800300)the Jiangsu Funding Program for Excellent Postdoctoral Talent。
文摘Lithium metal batteries(LMBs)are promising candidates for next-generation high-energy-density storage devices.However,an unstable lithium metal anode poses significant issues that critically compromise battery safety and cycle life,including lithium dendrite formation,solid electrolyte interphase degradation,dead lithium accumulation,and substantial volume fluctuations during cycling.These problems can be addressed by regulating lithium deposition and suppressing side reactions through the modification of copper current collectors using three classes of materials:metal and metal oxide,carbon,and polymer materials.This review comprehensively examines recent advances in the application of these materials as current collector coatings.Particularly,their distinct roles in the lithium deposition process are analyzed to understand how they mitigate the issues associated with the lithium metal anode.Furthermore,their inherent limitations are considered to inform future research directions.While each class of materials offers specific advantages,multifunctionality is required to effectively regulate lithium deposition.In prospect,a novel composite copper current collector design that integrates the merits of the aforementioned advanced materials is proposed.The insights from this review provide valuable guidance for the rational design of modified copper current collectors,which would significantly improve the safety and cycle life of LMBs and advance their commercialization.
基金supported by the Basic and Applied Basic Research Foundation of Guangdong province(2024A1515030155 and 2022A1515010272)Natural Science Foundation of China(61904067)+2 种基金Basic and Applied Basic Research Foundation of Guangzhou city(202102020758)Open funding from State Key Laboratory of Optoelectronic Materials and Technologies(Sun Yat-Sen University,OEMT2022-KF-08)Fundamental Research Funds for the Central Universities(11625109,11621405)。
文摘Metals,indispensable since the Bronze Age,remain pivotal in modern technologies due to their exceptional properties and versatility.Beyond traditional machining,advanced nano/micro-machining techniques enable the fabrication of metallic nano/micro structures with high precision in shape,size,and pattern.These structures endow flexible electrodes with outstanding electrical,mechanical,optical,and electrochemical performance,enabling growing applications in flexible optoelectronics,epidermal electronics,energy harvesting,and biochemical sensing.This review provides a comprehensive overview of the fabrication strategies for flexible electrodes made from metal meshes,metal nanowires,and liquid metals.The current advancements,existing challenges,and emerging technologies are systematically discussed.Furthermore,the progression toward ultra-thin,soft epidermal electrodes is explored,with an emphasis on novel in situ and transfer fabrication methods.We examine the underlying mechanisms,performance indicators,and their integration for on-skin applications,including bioelectric sensing,electrical stimulation,and energy harvesting.Finally,we highlight the remaining challenges in performance improvement and industrialization of flexible and epidermal electrodes,along with future opportunities for integrating multimodal systems and leveraging artificial intelligence to enhance their functionalities.
基金supported by the National Natural Science Foundation of China,No.82460711Science and Technology Foundation of Guizhou Province,No.ZK[2021]-014(both to FZ).
文摘Neurodegenerative diseases,which mainly include Alzheimer’s disease,Parkinson’s disease,amyotrophic lateral sclerosis,Wilson’s disease,and Huntington’s disease,are a group of disorders characterized by loss of neurons in the brain and spinal cord.However,the underlying pathogenetic mechanisms of these disorders remain unclear.The metal ion hypothesis is considered a possible cause of a variety of neurodegenerative diseases.This hypothesis posits that the homeostatic imbalance of metal ions leads to oxidative stress,neuroinflammation,excessive aggregation of pathological proteins,and other serious consequences in neurons.The powerful endogenous metal ion chelator metallothionein plays an important role in regulating metal ion homeostasis to alleviate neurodegenerative diseases.This article provides an overview of the pathogenesis of neurodegenerative diseases in relation to metal ions such as copper,iron,and zinc and the contribution of metallothionein to the regulation of metal ion homeostasis.The review focuses on the role of metal ions in the course of neurodegenerative diseases and the molecular mechanisms through which endogenous metallothionein ameliorates metal ion overload to alleviate neurodegenerative diseases.A thorough understanding of these molecular mechanisms can provide a theoretical foundation for the development of new therapeutic strategies,with the aim of more effectively treating these devastating diseases in the future.
基金supported by the Development Program of China and the National Key Research (Grant Nos.2023YFA1406200 and 2022YFA1402304)the National Natural Science Foundation of China (Grant Nos.12274169 and 12122405)+3 种基金the Fundamental Research Funds for the Central Universitiesthe Innovation Team for Functional Materials and Devices for Informatics at Anhui Higher Education Institutes (Grant No.2024AH010024)the Natural Science Research Project of Education Department of Anhui Province (Grant No.2025AHGXZK31203)the PHD Research Startup Foundation of Fuyang Normal University (Grant No.2025KYQD0072)。
文摘The Kagome metal CsV3Sb5 transitions from a weakly correlated state to a strongly correlated state upon Cr substitution;however,the mechanism driving this enhancement remains an open question.Here,we employed a combination of density functional theory and dynamical mean-field theory(DFT+DMFT)to systematically investigate the evolution of electronic correlations in the CsV_(3−x)Cr_(x)Sb_(5)(x=0,1,and 3)series.Our calculations revealed that Cr doping drives the system into a strongly correlated Hund’s metal phase,which is characterized by significant and orbital-dependent enhancements in the quasiparticle effective masses and electronic scattering rates.We trace the origin of this transition to the doping-induced shift from low-to high-spin atomic configurations.This preference for high-spin states,which is promoted by near-half-filling of the Cr-d orbitals,induces a pronounced orbital blocking effect that strengthens the correlations.Our findings establish that Hund’s coupling is the decisive factor governing the rich correlation physics in the CsV_(3−x)Cr_(x)Sb_(5) family,providing a tunable platform for exploring Hund’s metallicity.
基金supported by’regional innovation mega project’program through the Korea Innovation Foundation funded by Ministry of Science and ICT(2710033465)the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(RS-2025-25441256)。
文摘Lithium metal anodes are promising for next-generation high-energy batteries,but their practical application is limited by safety issues arising from uncontrolled Li metal growth.To address these challenges,we report a scalable approach to fabricate flexible,free-standing 3D carbon textiles derived from low-cost cellulose textiles,uniformly decorated with cobalt particles(Co@c-Textile).The work function difference between cobalt particles and carbon induces a redistribution of surface charge,enabling the synergistic combination of cobalt and defective carbon to enhance lithiophilicity and promote uniform Li growth through accelerate surface diffusion.Detailed analyses further reveal that lithium preferentially plates not directly on the cobalt particles,but on the adjacent carbon regions,eventually encapsulating the cobalt and growing uniformly across the carbon surface.As a result,the Co@c-Textile@Li anode exhibits prolonged and stable cycling over 700 h in symmetric cells,along with improved Li+transport kinetics.Furthermore,in full-cells with Li Fe PO_(4)(LFP)cathodes,it delivers over 90%capacity retention at both1C and 4C,and also demonstrates excellent stability under high-voltage conditions with Ni-rich cathodes.These findings clarify the role of transition metal/carbon composites in directing uniform Li plating and provide a viable strategy for designing advanced carbon-hosted Li metal anodes.
