Zeitschrift für anorganische und allgemeine Chemie最新文献

Oxygen redox activity in battery cathodes and the role of underbonded oxygen 电池阴极中的氧氧化还原活性和欠键氧的作用

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-09-18 DOI: 10.1002/zaac.202400067

Anthony West, Yangyang Roy Zhao, Laurence Roy Middlemiss, Xuan Roy Zhi, Peter Roy Gross

{"title":"Oxygen redox activity in battery cathodes and the role of underbonded oxygen","authors":"Anthony West, Yangyang Roy Zhao, Laurence Roy Middlemiss, Xuan Roy Zhi, Peter Roy Gross","doi":"10.1002/zaac.202400067","DOIUrl":"https://doi.org/10.1002/zaac.202400067","url":null,"abstract":"It is widely recognised that oxygen redox makes a significant contribution to the high capacity of some cathode materials in addition to transition metal redox. We attribute this to the presence of underbonded oxide ions, either in bulk structures or at surfaces, which are the initial source of oxygen redox during charging. Underbonded oxide ions experience departures from local electroneutrality; examples include Li4Mn5O12 spinel and Li‐rich layered rock salt structures but not stoichiometric LiCoO2 or Li2MnO3. Underbonded oxide ions ionise more readily than fully‐stabilised lattice oxide ions since, using an ionic bonding description, they are associated with a deficiency of positive charge in the coordination sphere of surrounding cations. Pauling’s electrostatic bond strength criterion gives a simple guide to structures or compositions that show departures from local electroneutrality and provides the starting point for a new way to consider oxygen redox. Li4Mn5O12 behaves as an anode due to Mn redox below 3V and as a cathode due to reversible oxygen redox above ~3.8 V. Underbonded oxygens are also identified in other structures, including high capacity Li‐rich layered rock salt structures.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"18 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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High‐Pressure Synthesis and Crystal Structure of the Inoborate Ni[B2O2(OH)4] 铌酸镍[B2O2(OH)4]的高压合成及其晶体结构

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-09-09 DOI: 10.1002/zaac.202400137

Leonard Conrad Pasqualini, Hubert Huppertz

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Synthesis and Single Crystal X‐ray Characterization of [Sn5Bi3]3− Sn5Bi3]3- 的合成与单晶 X 射线表征

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-09-09 DOI: 10.1002/zaac.202400086

Ute Friedrich, Franz Schmidt, Nikolaus Korber

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Chiral Homodinuclear Dysprosium Macrocyclic Complexes with Single‐molecule Magnetic Behaviours 具有单分子磁性的手性同核大环镝配合物

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-09-07 DOI: 10.1002/zaac.202400139

Zi-Hang Cheng, Ru-Chan Liu, Feng Gao

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Supramolecular Interactions as Key in Racemic Resolution: New Insights into the (SSi)‐ and (RSi)‐Diastereomers of (1R,2S,5R)‐Methyl(1‐naphthyl)‐phenylmenthoxysilane of Sommer 超分子相互作用是外消旋解析的关键：索默(1R,2S,5R)-甲基(1-萘基)-苯基薄荷硅烷的(SSi)-和(RSi)-非对映异构体的新见解

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-09-02 DOI: 10.1002/zaac.202400135

Jan-Lukas Kirchhoff, Carsten Strohmann

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From tin(II) to tin(IV): Following solid‐liquid reactions by microscopy 从锡(II)到锡(IV)：用显微镜跟踪固液反应

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-09-02 DOI: 10.1002/zaac.202400091

Hans Reuter, Simona Schröder, Natalie Röwekamp-Krugley, Markus Imwalle

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Syntheses, structures, properties, and calculation of a family of ionic crystals based on 1,3‐bis(5‐tetrazolyl)triazene 基于 1,3-双(5-四唑基)三氮烯的离子晶体家族的合成、结构、特性和计算

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-29 DOI: 10.1002/zaac.202400049

Bin Liu, Liang He, Zi-chen Shi, Wen-hui Huang, Qi Xue, Jian-hui Yang

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Structure prediction and mechanical properties of tantalum carbide (TaC) on ab initio level 碳化钽（TaC）的结构预测和力学性能的原初水平

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-23 DOI: 10.1002/zaac.202400088

Dejan Zagorac, Jelena Zagorac, Tamara Škundrić, Milan Pejić, Dušica Jovanović, J. Christian Schön

{"title":"Structure prediction and mechanical properties of tantalum carbide (TaC) on ab initio level","authors":"Dejan Zagorac, Jelena Zagorac, Tamara Škundrić, Milan Pejić, Dušica Jovanović, J. Christian Schön","doi":"10.1002/zaac.202400088","DOIUrl":"https://doi.org/10.1002/zaac.202400088","url":null,"abstract":"Tantalum carbide (TaC) is an extremely hard, brittle, refractory ceramic material with excellent physical properties, which makes it a desirable material in e.g. aerospace industries. In order to explore the range of feasible modifications of TaC, we have executed a crystal structure prediction study of the TaC chemical system using a multi‐methodological approach, via enthalpy landscape explorations of pristine TaC at different pressures, supplemented by data mining searches in the ICSD database. Local structure relaxations have been accomplished by using Density Functional Theory (DFT). The global minimum is found to correspond to the equilibrium rock salt (NaCl) type modification. Additionally, eight new phases of tantalum carbide are predicted to be feasible: the WC‐type, the NiAs‐type, the 5‐5‐type, the ZnS‐type, the Ring_TaC‐type, the CsCl‐type, the Ortho_TaC‐type, and the Tetra_TaC‐type. Furthermore, the elastic and mechanical properties of the predicted TaC modifications were explored on the DFT level of computation. The promising values of some of the mechanical properties of the proposed tantalum carbide modifications suggest that various scientific, industrial and technological applications of TaC should be possible.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"65 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Facile mechanochemical synthesis of compositionally complex spinel‐type oxides, (Co, Fe, Mn)3O4, (Co, Fe, Mn, Ni)3O4, (Co, Cr, Fe, Mn, Ni)3O4 成分复杂的尖晶石型氧化物 (Co、Fe、Mn)3O4、(Co、Fe、Mn、Ni)3O4、(Co、Cr、Fe、Mn、Ni)3O4 的简便机械化学合成方法

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-22 DOI: 10.1002/zaac.202400134

Dharma Teja Teppala, Jan Bernauer, Esteve Drouillard, Yaswanth Kumar Geddam, Guoxing Chen, Marc Widenmeyer, Maximilian Trapp, Hans-Joachim Kleebe, Ravi Kumar, Sanjay Mathur, Emanuel Ionescu

{"title":"Facile mechanochemical synthesis of compositionally complex spinel‐type oxides, (Co, Fe, Mn)3O4, (Co, Fe, Mn, Ni)3O4, (Co, Cr, Fe, Mn, Ni)3O4","authors":"Dharma Teja Teppala, Jan Bernauer, Esteve Drouillard, Yaswanth Kumar Geddam, Guoxing Chen, Marc Widenmeyer, Maximilian Trapp, Hans-Joachim Kleebe, Ravi Kumar, Sanjay Mathur, Emanuel Ionescu","doi":"10.1002/zaac.202400134","DOIUrl":"https://doi.org/10.1002/zaac.202400134","url":null,"abstract":"In the current work, a simple mechanochemical route has been employed to preparatively access three spinel‐type compositionally complex ceramics, i.e., (Co, Fe, Mn)3O4, (Co, Fe, Mn, Ni)3O4, and (Co, Cr, Fe, Mn, Ni)3O4. Hydrated nitrate salts of the respective transition metal elements were mechanically ground with ammonium hydrogen carbonate. The resulting paste‐like mixture of metal hydroxides, oxyhydroxides, and carbonates was rinsed with water to remove the byproduct (NH4NO3) and converted into the respective single‐phase spinel‐type oxides via calcination. In situ X‐ray diffraction (XRD) revealed the formation of the spinel‐type structure (Fdm) already at temperatures as low as 150 °C. Typically, the calcination of the precursors at temperatures beyond 500 °C led to the formation of well‐crystallized, single‐phase spinel‐type oxides with nearly equimolar composition and highly homogeneous distribution of the transition metals within the structure. The mechanochemical synthesis route in the present study is considered to be an easy, straightforward, and scalable access to compositionally complex oxides.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"74 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Coordination Networks from [Te4]2+ Clusters and Polynitriles 来自 [Te4]2+ 簇和多腈的配位网络

Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-08-21 DOI: 10.1002/zaac.202400112

Johannes Beck, Thomas Bredow, Jörg Daniels, Marcus Zink, Doris Ernsthäuser, Dominik Thönnes

{"title":"Coordination Networks from [Te4]2+ Clusters and Polynitriles","authors":"Johannes Beck, Thomas Bredow, Jörg Daniels, Marcus Zink, Doris Ernsthäuser, Dominik Thönnes","doi":"10.1002/zaac.202400112","DOIUrl":"https://doi.org/10.1002/zaac.202400112","url":null,"abstract":"The reactions of a series of organic polynitriles with [Te4][AsF6]2 in liquid SO2 solution lead either to reduction of [Te4]2+ to elemental tellurium or to the formation of coordination polymers. With 1,3‐dicyanobenzene (1,3‐DCB), 1,4‐dicyanobenzene (1,4‐DCB), 1,2,4,5‐tetracyanobenzene (TCB), tetracyanoethylene (TCNE) and tetracyanochinodimethane (TCNQ) the coordination complexes [Te4][AsF6]2 · 2(1,3‐DCB), [Te4][AsF6]2 · 3(1,4‐DCB) · 2SO2, [Te4][AsF6]2 · TCB, [Te4][AsF6]2 · TCNE and [Te4][AsF6]2 · TCNQ · 8SO2 were isolated and characterized by crystal structure analyses and vibrational Raman spectroscopy. The nitriles are coordinated to the square‐planar clusters forming 1D chains, 2D arrangements and 3D networks. Tetrakis(dicyanomethylene)‐cyclobutendiide [C4(C{CN}2)4]2‒ is oxidized by [Te4]2+ to the neutral cyanocarbon C4(C{CN}2)4 structurally representing a 4[radialene]. The ionization potentials and electron affinities of the cyanamide anion, cyanogen, 1,2‐DCB, 1,3‐DCB, 1,4‐DCB, TCB, C4(C{CN}2)4, TCNE and TCNQ and those polynitriles, which cause reduction of [Te4]2+, were calculated at coupled‐cluster level of theory in order to examine possible reasons for the stability of the coordination polymers based on electronic properties of the nitriles.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":"24 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142190641","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0