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Chinese Journal of Chemistry 2024年第6期42卷 617-622页

作者： Wei-Xing Chen Yu-He Xu Cui-Cui Wang Lei Qiao Zi-Yan Guo Wen-Juan Tian Zhong-Ming Sun state key laboratory of Element-Organic Chemistry Tianjin Key Lab for Rare Earth Materials and ApplicationsSchool of Materials Science and EngineeringNankai UniversityTianjin300350 China Institute of Molecular Science Shanxi UniversityTaiyuanShanxi030006 China

Binary polyantimony clusters,namely[Cu_(2)Sb_(14)]^(4–) and [Ag_(2)Sb_(14)]^(4–),containing coinage metals,were successfully synthesized and characterized,in which two homoatomic Sb73–subunits are bridged by two coinage metals in η^(4):η^(1) and η^(1):η^(1) coordination modes,***[M_(2)Sb_(14)]^(4-),two bridging Cu ions and two Sb atoms form a planar rhombic unit,which was revealed to have antiaromatic properties by theoretical *** electron structure and bonding analysis confirmed the presence of delocalized bonds in the rhombic unit and the metallophilic interaction between two formal M^(+) ions.

关键词： Polyantimony cluster Copper Silver Antiaromaticity Metallophilic interaction Quantum chemical calculations

The first chiral cerium halide towards circularly-polarized luminescence in the UV region

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Science China Chemistry 2024年第6期67卷 1961-1968页

作者： Xinyi Niu Zhichao Zeng Zhaoyu Wang Haolin Lu Bing Sun Hao-Li Zhang Yongsheng Chen Yaping Du Guankui Long Tianjin key Lab for rare earth materials and applications Renewable Energy Conversion and Storage CenterSmart Sensing Interdisciplinary Science CenterSchool of Materials Science and EngineeringNational Institute for Advanced MaterialsNankai UniversityTianjin300350China Tianjin key Lab for rare earth materials and applications Center for Rare Earth and Inorganic Functional MaterialsHaihe Laboratory of Sustainable Chemical TransformationsSmart Sensing Interdisciplinary Science CenterSchool of Materials Science and EngineeringNational Institute for Advanced MaterialsNankai UniversityTianjin300350China state key laboratory of Applied Organic Chemistry Key Laboratory of Special Function Materials and Structure Design(Ministry of Education)College of Chemistry and Chemical EngineeringLanzhou UniversityLanzhou730000China The Centre of Nanoscale Science and Technology and state key laboratory of Elemento-Organic Chemistry Frontiers Science Center for New Organic MatterCollege of ChemistryNankai UniversityTianjin300071China

Chiral organic-inorganic hybrid metal halides(OIHMHs)have attracted broader scientific community recently in spin lightemitting diodes,and circularly polarized light-emitting ***,the emission peaks of the reported chiral OIHMHs mainly locate in the visible region,and chiral OIHMH with ultraviolet(UV)circularly polarized luminescence(CPL)has been rarely *** fill this gap,cerium,a unique rare-earth(RE)element with tunable luminescence from UV to the visible region owing to the 4 f-related electronic transition,was introduced to construct the first RE-based chiral OIHMHs,R/*** chirality is successfully transferred from the chiral organic cations to the inorganic cerium chloride framework in R/S-MCC,as confirmed by the single crystal structures,circular dichroism,and *** emission spectra of R/S-MCC are in the UV region,originating from the characteristic d-f transition of Ce^(3+),which making the Ce-based metal halides are ideal candidates towards CPL light sources in the UV ***,R-and S-MCC are the first RE-based OIHMHs,also the first chiral metalhalides with UV *** work opens a new avenue for the development of the chiral OIHMH family towards RE-based chiral *** RE-based chiral metal halides couple the unique and superior optical,electrical,magnetic,and spintronic properties of RE elements with chirality could accelerate the development of chiral optoelectronics and spintronics toward real applications.

关键词： chiral rare-earth halide ultraviolet circularly-polarized luminescence d-f transition rare-earth halide perovskite chiral perovskite

Facile and effective synthesis strategy for terbium-doped hydroxyapatite toward photoelectric devices and flexible functional fibers

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rare Metals 2024年第4期43卷 1713-1723页

作者： Xiao-Dong Zhang Kun Nie Zi-Yao Hu Ran-Ran Zhou Xiu-Qiang Duan Wu-Bin Dai Song-Song Nie Song-Jun Yao Luo-Xin Wang Le-Fu Mei Hua Wang Yi-Yi Yao Xiao-Xue Ma Hubei key laboratory for New Textile materials and applications and state key laboratory of New Textile materials and Advanced Processing Technology School of Materials Science and EngineeringWuhan Textile UniversityWuhan430200China key laboratory of Testing and Tracing of rare earth Products for state Market Regulation Jiangxi University of Science and TechnologyGanzhou341000China Hubei key laboratory of Plasma Chemistry and Advanced materials and key laboratory of Green Chemical Engineering Process of Ministry of Education Wuhan Institute of TechnologyWuhan430205China

As a material with good biocompatibility,hydroxyapatite(HAP)can have optical properties after doping with various rare earth *** a biocompatible fluorescent material,doped HAP could have broad applications in biological probes,drug delivery,optoelectronic materials,fluorescence anti-counterfeiting,and other *** this paper,we put forward the preparation of HAP doped with terbium(Ⅲ)ions(Tb^(3+))by hydrothermal *** controlling the Tb^(3+)doping content in reaction and the reaction time,the changes in HAP's structure,morphology,and luminescence properties under different conditions were *** the doping amount of Tb^(3+)reached an optimal value,the dipole-quadrupole would occur and the concentration would be *** control experiment showed that the optimal Tb3+content was 7.5×10^(-5)mol,which showed the best fluorescence ***,a non-luminous material,was rarely used in the field of fluorescent anti-counterfeiting and photoelectric *** proposed to prepare a luminescent aramid/polyphenylene sulfide(ACFs/PPS)fiber paper and a new light-emitting diode(LED)using the Tb-doped HAP *** composite sample exhibited an excellent stability and fluorescence performance,which also demonstrated a possibility of HAP applications in anticounterfeiting and *** introduction of Tb3+dopant HAP was done to give HAP optical properties and broaden the application range of HAP.

关键词： Hydroxyapatite rare earth luminescence Photoelectric device Aramid Polyphenylene sulfide fiber paper Luminescent fiber

Electrostatically connected nanoarchitected electrocatalytic films for boosted water splitting

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Nano Research 2024年第3期17卷 1114-1122页

作者： Chao-Peng Wang Hao Sun Gang Bian Jia-Xi Wang Xixi Pang Guoqi Wang Jian Zhu Xian-He Bu School of materials Science and Engineering National Institute for Advanced MaterialsNankai UniversityTianjin 300350China Tianjin key laboratory of Metal and Molecule-Based Material Chemistry Nankai UniversityTianjin 300350China Tianjin key laboratory for rare earth materials and applications Nankai UniversityTianjin 300350China

Active sites of two-dimensional(2D)electrocatalysts are often partially blocked owing to their inevitable stacking and hydrophobic polymeric binders in macroscale electrodes,therefore impeding their applications in efficient ***,using layered double hydroxide(LDH)nanosheets as a model 2D electrocatalyst,we demonstrate that their performance toward water splitting can be boosted when they are electrostatically assembled into an organized structure pillared by hydrophilic polyelectrolytes or nanoparticles in a layer-by-layer(LbL)*** particular,their mass activity on a planar electrode can be as large as 2.267 mA·μg^(-1) toward oxygen evolution reaction(OER),when NiFe-LDH nanosheets are electrostatically connected by poly(sodium 4-styrenesulfonate)(PSS),while drop-casted NiFe-LDH nanosheets only have a mass activity of 0.116 mA·μg^(-1).In addition,these homogeneous NiFe-LDH nanofilms can be easily deposited on three-dimensional(3D)surfaces with high areas,such as carbon cloths,to serve as practical electrodes with overpotentials of 328 mV at a current density of 100 mA·cm^(-2),and stability for 40 ***,Pt nanoparticles can be LbL assembled with NiFe-LDH as bifunctional electrodes for synergistically boosted oxygen and hydrogen evolution reactions(HER),leading to successful overall water splitting powered by a 1.5 V *** study heralds the spatial control of 2D nanomaterials in nanoscale precision as an efficient strategy for the design of advanced electrocatalysts.

关键词： layer-by-layer(LbL)assembly layered double hydroxides(LDH) two-dimensional(2D)electrocatalysts oxygen evolution reaction(OER) water splitting

Metal-metal bonds in Zintl clusters:Synthesis,structure and bonding in[Fe_(2)Sn_(4)Bi_(8)]^(3-)and[Cr_(2)Sb_(12)]^(3-)

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Chinese Chemical Letters 2024年第8期35卷 558-566页

作者： Ya-Nan Yang Zi-Sheng Li Sourav Mondal Lei Qiao Cui-Cui Wang Wen-Juan Tian Zhong-Ming Sun John E.McGrady state key laboratory of Element-Organic Chemistry Tianjin Key Lab for Rare Earth Materials and ApplicationsSchool of Materials Science and EngineeringNankai UniversityTianjin 300350China Department of Chemistry University of OxfordInorganic Chemistry LaboratoryOxfordOX13QRUnited Kingdom

We report here the synthesis and characterization of two new members of the M2 E 12 family of endohe-dral Zintl clusters,[Fe_(2)Sn_(4)Bi_(8)]^(3-)and[Cr_(2)Sb_(12)]^(3-),both of which contain open-shell metal dimers encap-sulated inside a triple-decker cluster of main-group *** 75-electron[Fe_(2)Sn_(4)Bi_(8)]^(3-)cluster has a D4h-symmetric structure,while[Cr_(2)Sb_(12)]^(3-),despite having the same 75-electron count,is strongly dis-torted to a geometry that resembles a CrSb_(8)crown capped by a CrSb_(4)*** structural differences between the two are driven by the increasing availability of 3d electron density in the earlier transi-tion metal,which leads,ultimately,to different electronic configurations in the two *** trends precisely mirror those observed in the ME_(10)and ME_(12)families containing a single transition metal ion.

关键词： Zintl anions Endohedral clusters Metal-metal bond Second-order Jahn-Teller effect DFT calculation

Pillar effect induced by ultrahigh phosphorous/nitrogen doping enables graphene/MXene film with excellent cycling stability for alkali metal ion storage

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Journal of Energy Chemistry 2024年第6期93卷 146-156,I0004页

作者： Meng Qin Yiwei Yao Junjie Mao Chi Chen Kai Zhu Guiling Wang Dianxue Cao Jun Yan key laboratory of Superlight materials and Surface Technology Ministry of EducationCollege of Materials Science and Chemical EngineeringHarbin Engineering UniversityHarbin 150001HeilongjiangChina Xiamen key laboratory of rare earth Photoelectric Functional materials and Xiamen Institute of Rare Earth MaterialsHaixi InstituteChinese Academy of SciencesXiamen 361021FujianChina

Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and long ion transfer ***,this paper aims to address the issue by introducing MXene through a simple and scalable method for assembling graphene and realizing ultrahigh P doping *** findings reveal that MXene and P-C bonds have a "pillar effect" on the structure of graphene,and the P-C bond plays a primary *** addition,N/P co-doping introduces abundant defects,providing more active sites for K^(+) storage and facilitating K^(+) *** expected,the developed ultrahigh phosphorous/nitrogen co-doped flexible reduced graphene oxide/MXene(NPrGM) electrode exhibits remarkable reversible discharge capacity(554 mA hg^(-1) at 0.05 A g^(-1)),impressive rate capability(178 mA h g^(-1) at 2 A g^(-1)),and robust cyclic stability(0.0005% decay per cycle after 10,000 cycles at 2 A g^(-1)).Furthermore,the assembled activated carbon‖NPrGM potassium-ion hybrid capacitor(PIHC) can deliver an impressive energy density of 131 W h kg^(-1) and stable cycling performance with 98.1% capacitance retention after5000 cycles at 1 A g^(-1).Such a new strategy will effectively promote the practical application of graphene materials in PIBs/PIHCs and open new avenues for the scalable development of flexible films based on two-dimensional materials for potential applications in energy storage,thermal interface,and electromagnetic shielding.

关键词： Graphene MXene Phosphorous doping Pillar effect Potassium-ion batteries

Study on the low mechanical anisotropy of extruded Mg-Zn-Mn-Ce-Ca alloy tube in the compression process

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Journal of Magnesium and Alloys 2024年第3期12卷 1054-1067页

作者： Dandan Li Qichi Le Xiong Zhou Xiaoqiang Li Chenglu Hu Ruizhen Guo Tong Wang Ping Wang Wenxin Hu The key laboratory of Electromagnetic Processing of materials Ministry of EducationNortheastern UniversityShenyang 110819China state key laboratory of Baiyunobo rare earth Resource Research and Comprehensive Utilization Baotou Research Institute of Rare EarthsBaotou 014030China

In this study,the extruded Mg-Zn-Mn-Ce-Ca alloy tube with a low compression anisotropy along the ED,45ED and TD was *** effect of the second phases,initial texture and deformation behavior on this low mechanical anisotropy was *** results revealed that the alloy tube contains the high content(Mg1-xZnx)11Ce phase and the low content of Mg12Ce *** second phases are respectively incoherent and coherent with the Mg matrix,and their influence can be ***,the alloy tube exhibited a weak basal fiber texture,where the c-axis was aligned along the 0°∼30°tilt from TD to *** a texture made the initial deformation(at 1.0%∼1.6%strain)of the three samples controlled by comparable basal*** deformation progressed(1.6∼9.0%strain),larger amounts of ETWs nucleated and gradually approached saturation in the three samples,re-orienting the c-axis to a 0°∼±30°deviation with respect to the loading ***,the prismatic and pyramidalslips replaced the dominant deformation progressively until ***,the similar deformation mechanisms determined by the weak initial texture in the three samples contribute to the comparable strain hardening rates,resulting in the low compressive anisotropy of the alloy tube.

关键词： Mg alloy tube Low mechanical anisotropy Weak texture Deformation mechanism.

Boosting ammonia production in electrocatalytic NO_(x)reduction on a robust Fe/FeMoO_(4)catalyst

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Nano Research 2024年第7期17卷 5801-5806页

作者： Dong-Xue Liu Xin Deng Yong-Fu Zhu Zhe Meng Xue-Feng Sun Miao-Miao Shi Hai-Xia Zhong Jun-Min Yan key laboratory of Automobile materials Ministry of EducationSchool of Materials Science and EngineeringJilin UniversityChangchun 130022China state key laboratory of rare earth Resource Utilization Changchun Institute of Applied ChemistryChinese Academy of SciencesChangchun 130022China

Electrocatalytic reduction of nitrate(NO_(3)^(−))and nitride(NO_(2)^(−))to ammonia(NH3)is of wide interest as a promising alternative to the energy-intensive Haber-Bosch route for mitigating the vast energy consumption and the accompanied carbon dioxide emission,as well as benefiting for the relevant sewage ***,exploring an efficient and low-cost catalyst with high atomic utilization that can effectively facilitate the slow multi-electron transfer process remains a grand ***,we present an efficient hydrogenation of NO_(3)^(−)/NO_(2)^(−)species to NH3 in both alkaline and neutral environments over the Fe_(2)(MoO_(4))_(3)derived hybrid electrocatalyst with the metallic Fe site on FeMoO_(4)(Fe/FeMoO_(4)).The Mo ingredient can play a synergistically positive role in further promoting the NH_(3) production on *** a result,Fe/FeMoO_(4)behaves well in the electrochemical NH_(3) generation from NO_(2)^(−)with a maximum NH_(3) Faradaic efficiency(FE)of 96.53%and 87.68%in alkaline and neutral electrolyte,corresponding to the NH_(3) yield rate of 640.68 and 302.56 mg·h^(−1)·mg_(cat.)^(−1),respectively,which outperforms the Fe and Mo counterpart and other similar catalyst,showing the robust catalytic capacity of each active site.

关键词： ammonia synthesis NO_(x)reduction synergistic effect alkaline/neutral electrolyte

Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid

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International Journal of Minerals,Metallurgy and materials 2024年第4期31卷 688-696页

作者： Haijun Yu Dongxing Wang Shuai Rao Lijuan Duan Cairu Shao Xiaohui Tu Zhiyuan Ma Hongyang Cao Zhiqiang Liu Institute of Advanced Wear&Corrosion Resistant and Functional materials Jinan UniversityGuangzhou 510632China Institute of Resources Utilization and rare earth Development Guangdong Academy of SciencesGuangzhou 510650China state key laboratory of Separation and Comprehensive Utilization of rare Metals Guangzhou 510650China Guangdong Province key laboratory of rare earth Development and Application Guangzhou 510650China

Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the *** methods usually are followed by a series of separation steps such as precipitation,extraction,and stripping to separate the individual valuable *** this study,we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic *** optimal leaching conditions(leaching time of 1.5 h,leaching temperature of 70°C,liquid-solid ratio of 4 mL/g,oxalic acid ratio of 1.3,and sulfuric acid ratio of 1.3),the lithium leaching efficiency reached89.6%,and the leaching efficiencies of Ni,Co,and Mn were 12.8%,6.5%,and 21.7%.X-ray diffraction(XRD)and inductively coupled plasma optical emission spectrometer(ICP-OES)analyses showed that most of the Ni,Co,and Mn in the raw material remained as solid residue oxides and *** study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.

关键词： selective leaching oxalic acid sulfuric acid spent lithium-ion batteries

Polarization engineering in porous organic polymers for charge separation efficiency and its applications in photocatalytic aerobic oxidations

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Science China Chemistry 2024年第3期67卷 1000-1007页

作者： Kun Wu Pei-Wen Cheng Xin-Yi Liu Ji Zheng Xiao-Wei Zhu Mo Xie Puxin Weng Weigang Lu Dan Li College of Chemistry and materials Science Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and ApplicationsJinan UniversityGuangzhou 510632China Guangdong rare earth Photofunctional materials Engineering Technology Research Center School of Chemistry and EnvironmentJiaying UniversityMeizhou 514015China

Photocatalytic aerobic oxidation reactions are largely governed by the efficiency of charge separation and subsequent reactive oxygen species(ROS) generation. Herein, we report a polarization engineering strategy to promote the charge separation and ROS generation efficiency by substituting the benzene unit with furan/thiophene in porous organic polymers(POPs). Benefiting from the extent of local polarization, the thiophene-containing POP(JNU-218) exhibits the best photocatalytic performance in aerobic oxidation reactions, with a yield much higher than those for the furan-containing POP(JNU-217) and the benzenecontaining POP(JNU-216). Experimental studies and theoretical calculations reveal that the increase of local polarization can indeed reduce the exciton binding energy, and therefore facilitate the separation of electron-hole pairs. This work demonstrates a viable strategy to tune charge separation and ROS generation efficiency by modulating the dipole moments of the building blocks in porous polymeric organic semiconductors.

关键词： porous organic polymer local polarization photocatalytic aerobic oxidation charge separation reactive oxygen species exciton binding energy