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On-surface synthesis and characterization of polyynic carbon chains

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National Science Review 2024年第3期11卷 192-199页

作者： Wenze Gao Wei Zheng Luye Sun Faming Kang Zheng Zhou Wei Xu Interdisciplinary materials research Center School of Materials Science and Engineering Tongji University

Carbyne, an elusive sp-hybridized linear carbon allotrope, has fascinated chemists and physicists for decades. Due to its high chemical reactivity and extreme instability, carbyne was much less explored in contrast to the sp2-hybridized carbon allotropes such as graphene. Herein, we report the on-surface synthesis of polyynic carbon chains by demetallization of organometallic polyynes on the Au（111） surface;the longest one observed consists of ～60 alkyne units（120 carbon atoms）. The polyynic structure of carbon chains with alternating triple and single bonds was unambiguously revealed by bond-resolved atomic force microscopy. Moreover, an atomically precise polyyne, C14, was successfully produced via tip-induced dehalogenation and ring-opening of the decachloroanthracene molecule(C14Cl10) on a bilayer NaCl/Au（111） surface at 4.7 K, and a band gap of 5.8 eV was measured by scanning tunnelling spectroscopy,in a good agreement with the theoretical HOMO–LUMO gap（5.48 eV）.

关键词： polyyne scanning probe microscopy carbon allotrope on-surface synthesis organometallic polyyne

Tendencies of alloyed engineering in BiOX-based photocatalysts:a state-of-the-art review

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Rare Metals 2024年第4期43卷 1488-1512页

作者： Yan-Dong Sun Chao Zeng Xue Zhang Zi-Qi Zhang Bo Yang Sheng-Qi Guo Tianjin Key Laboratory of Clean Energy and Pollutant Control School of Energy and Environmental EngineeringHebei University of Technology State-Province Joint engineering Laboratory of Zeolite membrane materials Institute of Advanced MaterialsCollege of Chemistry and Chemical EngineeringJiangxi Normal University Anhui Province Key Laboratory of Pollutant Sensitive materials and Environmental Remediation School of Physics and Electronic InformationAnhui Province Industrial Generic Technology Research Center for Alumics MaterialsHuaibei Normal University

Energy-saving and environmentally friendly photocatalysis has emerged as a popular research area in response to issues with energy scarcity and environmental degradation.Due to the unique layer-like structure,BiOX（Cl,Br,I） is frequently used in photocatalysis.However,inherent flaws in BiOX,such as an inappropriate band gap and low carrier separation efficiency,restrict its capacity for photocatalysis.Owing to the tunable grouping layer,alloying engineering is employed to optimize the intrinsic properties of BiOX and alloyed BiOX becomes a promising photocatalytic material.This review describes the structure of BiOX,where tunable halogen layers provide favorable conditions for the implementation of alloying engineering to improve intrinsic properties.The article compares the effects and mechanisms of alloying engineering on the optimization of the energy band structure and carrier behavior of BiOX,and lists various modification methods used to improve the optimization of the intrinsic properties by alloying engineering,including defect engineering,morphology control as well as the synergy between alloying and other modification methods（bismuth-rich strategies,cation doping,construction of heterojunctions and plasma resonance effects）.Subsequently,applications of alloyed BiOX in energy and environmental fields are summarized,including contaminant degradation,antibacterial,CO2reduction,nitrogen fixation and organic synthesis.Finally,we summarize the current challenges and future directions of alloyed BiOX.It is expected that this work will provide guidance and assistance for an in-depth study and understanding of the mechanisms of alloying engineering to optimize intrinsic properties and design alloyed BiOX with higher photocatalytic activity.

关键词： Bismuth oxyhalide Photocatalytic Alloyed engineering Microstructural regulation Application

Efficient and stable PtFe alloy catalyst for electrocatalytic methanol oxidation with high resistance to CO

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Journal of Energy Chemistry 2024年第3期90卷 327-336,I0008页

作者： Qian Yang Sifan Zhang Fengshun Wu Lihua Zhu Guang Li Mingzhi Chen An Pei Yingliang Feng jiangxi Provincial Key Laboratory of Functional Molecular materials Chemistry College of Chemistry and Chemical EngineeringFaculty of Materials Metallurgy and ChemistryJiangxi University of Science and TechnologyGanzhou 341000JiangxiChina College of Chemistry and Chemical engineering Xiamen UniversityXiamen 361005FujianChina

Direct methanol fuel cells(DMFC) are widely considered to be an ideal green energy conversion device but their widespread applications are limited by the high price of the Pt-based catalysts and the instability in terms of surface CO toxicity in long-term operation.Herein,the PtFe alloy nanoparticles(NPs) with small particle size(~4.12 nm) supported on carbon black catalysts with different Pt/Fe atomic ratios(Pt_(1)Fe_(2)/C,Pt_(3)Fe_(4)/C,Pt_(1)Fe_(1)/C,and Pt_(2)Fe_(1)/C) are successfully prepared for enhanced anti-CO poisoning during methanol oxidation reaction(MOR).The optimal atomic ratio of Pt/Fe for the MOR is 1:2,and the mass activity of Pt_(1)Fe_(2)/C(5.40 A mg_(Pt)^(-1)) is 13.5 times higher than that of conventional commercial Pt/C(Pt/C-JM)(0.40 A mg_(Pt)^(-1)).The introduction of Fe into the Pt lattice forms the PtFe alloy phase,and the electron density of Pt is reduced after forming the PtFe alloy.In-situ Fourier transform infrared results indicate that the addition of oxyphilic metal Fe has reduced the adsorption of reactant molecules on Pt during the MOR.The doping of Fe atoms helps to desorb toxic intermediates and regenerate Pt active sites,promoting the cleavage of C-O bonds with good selectivity of CO_(2)(58.1%).Moreover,the Pt_(1)Fe_(2)/C catalyst exhibits higher CO tolerance,methanol electrooxidation activity,and long-term stability than other Pt_(x)Fe_(y)/C catalysts.

关键词： Alloy catalyst PtFe Methanol oxidation In-situ FTIR CO resistance

Rationally construction of atomic-precise interfacial charge transfer channel and strong build-in electric field in nanocluster-based Zscheme heterojunctions with enhanced photocatalytic hydrogen production

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Nano research 2024年第6期17卷 5002-5010页

作者： Qingtao Zhu Honglei Shen Chao Han Liu Huang Yanting Zhou Yuanxin Du Xi Kang Manzhou Zhu Department of materials Science and engineering Centre for Atomic Engineering of Advanced MaterialsKey Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of EducationKey Laboratory of Functional Inorganic Material Chemistry of Anhui ProvinceAnhui UniversityHefei 230601China

The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.

关键词： atomically precise metal nanocluster Z-scheme heterojunction interfacial charge transfer build-in electric field photocatalytic hydrogen production

A novel Tb^(3+) and Eu^(3+) co-doped dual-emitting phosphate K_(3)SrBi(P_(2)O_(7))_(2) phosphor for application in FIR thermometers

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Journal of Rare Earths 2024年第3期42卷 455-463,I0001页

作者： Baochen Wang Shifeng Sun Zeqi Li Zongwang Li Weiwei Lin Chao Zeng Yan-gai Liu Ruiyu Mi School of Chemical and Environmental engineering Anhui Polytechnic UniversityWuhu241000China State-Province Joint engineering Laboratory of Zeolite membrane materials Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of EducationInstitute of Advanced MaterialsCollege of Chemistry and Chemical EngineeringJiangxi Normal UniversityNanchang330022China Beijing Key Laboratory of materials Utilization of Nonmetallic Minerals and Solid Wastes National Laboratory of Mineral MaterialsSchool of Materials Science and TechnologyChina University of GeosciencesBeijing100083China

Rare earth co-doped phosphor for fluorescence intensity ratio(FIR) thermometer has gained increasing attention in recent years. Herein, the novel Tb^(3+)and Eu^(3+)co-doped K_(3)SrBi(P_(2)O_(7))_(2)(KSBP) phosphate phosphors were reported. The crystal structure of the title phosphor was determined using Rietveld refinement and proved to have a three-dimensional structure. The time-resolved spectroscopy reveals that there is almost no energy transfer between Tb^(3+)and Eu^(3+). More importantly, Tb^(3+)and Eu^(3+)emissions show different thermal quenching behaviors, which claims the potential of this material for application in optical thermometer. The FIR of the typical KSBP:0.02Tb^(3+),0.04Eu^(3+)sample demonstrates a polynomial relationship as a function of temperature and the absolute and relative sensitivity are0.025 K^(-1) and 0.59%/K, respectively. In general, our study reports a novel and potential KSBP:Tb^(3+),Eu^(3+)phosphate phosphor that is promising for use in high-sensitive FIR thermometers.

关键词： Phosphor Thermometer Fluorescence intensity ratio Thermal stability Rare earths

Magnetic, dielectric and luminescence synergetic switchable effects in molecular material [Et_(3)NCH_(2)Cl]_(2)[MnBr_(4)]

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Chinese Chemical Letters 2024年第4期35卷 502-505页

作者： Yan Cheng Hua-Peng Ruan Yan Peng Longhe Li Zhenqiang Xie Lang Liu Shiyong Zhang Hengyun Ye Zhao-Bo Hu Chaotic Matter Science research Center Faculty of Materials Metallurgy and ChemistryJiangxi University of Science and TechnologyGanzhou 341000China College of materials and Chemical engineering Pingxiang UniversityPingxiang 337055China jiangxi Provincial Key Laboratory of Functional Molecular materials Chemistry Jiangxi University of Science and TechnologyGanzhou 341000China Key Laboratory of jiangxi University for Functional materials Chemistry School of Chemistry and Chemical EngineeringGannan Normal UniversityGanzhou 341000China

The application of multifunctional materials in various fields such as electronics and signal processors has attracted massive attention. Herein, a new organic-inorganic hybrid material [Et_(3)NCH_(2)Cl]_(2)[MnBr_(4)](1) is reported, which contains two organic amines cations and one [MnBr_(4)] tetrahedral ion. Compound 1 has a dielectric anomaly signal at 338 K, which proves its thermodynamic phase transition. The single crystal measurements at 200 K and 380 K show that the phase transition of compound 1 is caused by the thermal vibration of organic amine cations in the lattice. Moreover, compound 1 shows yellow-green luminescence under UV light irradiation. The magnetism measurements indicate that compound 1 shows switchable magnetic properties. This organic–inorganic material is a multifunctional material with dielectric, optical, and magnetic synergetic switchable effects, which expands a new direction for designing multifunctional materials.

关键词： Synergetic switchable effects Molecular materials Magnetism Dielectric Luminescence

Defects in the grain interiors of 3 mol%yttria-stabilized tetragonal zirconia polycrystal ceramics with 0.25 wt%alumina

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Journal of Advanced Ceramics 2024年第4期13卷 469-477页

作者： Yan Xiong Lian Luo Yao Cheng Zhi Liu Qi Liu Weimin Wang Wei Ji School of materials&Chemical engineering Hubei Province Key Laboratory of Green Materials for Light IndustryHubei University of TechnologyWuhan 430068China Fujian Institute of research on the Structure of Mater Chinese Academy of SciencesFuzhou 350002China jiangxi Provincial engineering research Center for Multifunction Zirconia materials Jiangxi Size Materials Co.Ltd.Jiujiang 332500China State Key Laboratory of Advance Technology for materials Synthesis and Processing Wuhan University of TechnologyWuhan 430070China

The presence of high-density defects is rarely observed in bulk 3 mol%yttria-stabilized tetragonal zirconia polycrystal(3Y-TZP)ceramics obtained through conventional pressureless sintering.In the present work,fine-grained dense 147 nm 3Y-TZP ceramics were prepared by pressureless sintering of commercial 0.25 wt%alumina-doped zirconia powders at 1300℃.A novel discovery was reported in which large amounts of defects were present in the grain interiors of the sample.The phenomenon was further examined using three types of powder samples,and the reasons for defect formation were investigated by microstructural characterization using high-resolution transmission electron microscopy(HRTEM)analysis and Rietveld refinement.The results confirmed the essential dependence of the defect formation on the alumina addition.The authors attributed the defect formation to the significant difference in ionic radii of the solvent and solute during the dissolution of alumina into the zirconia lattice.The sintering kinetics were proposed to be enhanced by the presence of substantial defects,which consequently favored the low-temperature sintering of the alumina-doped zirconia ceramics.

关键词： 3 mol%yttria-stabilized tetragonal zirconia polycrystal(3Y-TzP)ceramics alumina addition microstructure defect

Microstructure evolution and mechanical properties of brazing joint for ultra-thin-walled Inconel 718 considering grain size effect and brazing temperature

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Chinese Journal of Aeronautics 2024年第2期37卷 541-556页

作者： Rui ZHAO Yueshuai SONG Hui KANG Min WAN School of Mechanical engineering and Automation Beihang UniversityBeijing 100191China jiangxi research Institute of Beihang University Jiangxi 330000China

The systematic investigation of the mechanical properties and microstructure evolution process of ultra-thin-walled Inconel 718 capillary brazing joints is of great significance because of the exceptionally high demands on its application.To achieve this objective,this study investigates the impact of three distinct brazing temperatures and five typical grain sizes on the brazed joints’mechanical properties and microstructure evolution process.Microstructural evolution analysis was conducted based on Electron Back Scatter Diffraction(EBSD),Scanning Electron Microscopy(SEM),X-Ray Diffraction(XRD),High-Resolution Transmission Electron Microscopy(HRTEM),and Focused Ion Beam(FIB).Besides,the mechanical properties and fracture behavior were studied based on the uniaxial tension tests and in-situ tension tests.The findings reveal that the brazing joint’s strength is higher for the fine-grain capillary than the coarse-grain one,primarily due to the formation of a dense branch structure composed of G-phase in the brazing seam.The effects of grain size,such as pinning and splitting,are amplified at higher brazing temperatures.Additionally,micro-cracks initiate around brittle intermetallic compounds and propagate through the eutectic zone,leading to a cleavage fracture mode.The fracture stress of fine-grain specimens is higher than that of coarse-grain due to the complex micro-crack path.Therefore,this study contributes significantly to the literature by highlighting the crucial impact of grain size on the brazing properties of ultra-thin-walled Inconel 718 structures.

关键词： EYWORDS Ultra-thin-walled structure Brazing Inconel 718 Grain size effect Brazing temperature

Modified constitutive models for Inconel 718 considering current density and temperature in electrically assisted forming process

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Chinese Journal of Aeronautics 2024年第2期37卷 524-540页

作者： Xuan CUI Rui ZHAO Min WAN School of Mechanical engineering and Automation Beihang UniversityBeijing 100191China jiangxi research Institute of Beihang University Jiangxi 330000China

Electrically Assisted Forming(EAF)technology has obvious advantages in material forming.To develop an effective constitutive model considering electrical effects,room temperature and electrically assisted quasi-static uniaxial tensile tests were conducted using ultrathin nickelbased superalloy plates with a thickness of 0.25 mm.The research focused on the two most widely recognized effects:the Joule thermal and the electric athermal effects.The mechanism of current action can be divided into two scenarios:one considering the Joule thermal effect only,and the other considering both effects simultaneously.Two basic constitutive models,namely the Modified-Hollomon model and the Johnson-Cook(J-C)model,were selected to be optimized through the classification of two different situations,and four optimized constitutive models were proposed.It was found that the J-C model with simultaneous consideration of the Joule thermal effect and electric athermal effect had the best prediction effect by comparing the results of these four models.Finally,the accuracy of the optimization model was verified by finite element simulation of the electrically assisted stretching optimization model.The results show that the constitutive model can effectively predict the temperature effect caused by the Joule heat effect and the athermal effect of current on the material.

关键词： Joule heating Elastoplasticity Plastic deformation Superalloys Constitutive models