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Effect of Dynamical Motion in ab Initio Calculations of Solid-State Nuclear Magnetic and Nuclear Quadrupole Resonance Spectra 固态核磁共振和核四极共振谱ab Initio 计算中的动力运动效应
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-19 DOI: 10.1021/acs.chemmater.4c00883
Kamal Wagle, Daniel A. Rehn, Ann E. Mattsson, Harris E. Mason, Michael W. Malone
Solid-state nuclear magnetic resonance (SSNMR) and nuclear quadrupole resonance (NQR) spectra provide detailed information about the electronic and atomic structure of solids. Modern ab initio methods such as density functional theory (DFT) can be used to calculate NMR and NQR spectra from first-principles, providing a meaningful avenue to connect theory and experiment. Prediction of SSNMR and NQR spectra from DFT relies on accurate calculation of the electric field gradient (EFG) tensor associated with the potential of electrons at the nuclear centers. While static calculations of EFGs are commonly seen in the literature, the effects of dynamical motion of atoms in molecules and solids have been less explored. In this study, we develop a method to calculate EFGs of solids while taking into account the dynamics of atoms through DFT-based molecular dynamics simulations. The method we develop is general, in the sense that it can be applied to any material at any desired temperature and pressure. Here, we focus on application of the method to NaNO2 and study in detail the EFGs of 14N, 17O, and 23Na. We find in the cases of 14N and 17O that the dynamical motion of the atoms can be used to calculate mean EFGs that are in closer agreement with experiments than those of static calculations. For 23Na, we find a complex behavior of the EFGs when atomic motion is incorporated that is not at all captured in static calculations. In particular, we find a distribution of EFGs that is influenced strongly by the local (changing) bond environment, with a pattern that reflects the coordination structure of 23Na. We expect the methodology developed here to provide a path forward for understanding materials in which static EFG calculations do not align with experiments.
固态核磁共振(SSNMR)和核四极共振(NQR)光谱提供了有关固体电子和原子结构的详细信息。密度泛函理论 (DFT) 等现代自创方法可用于从第一原理计算 NMR 和 NQR 光谱,为理论与实验之间的联系提供了一条有意义的途径。利用 DFT 预测 SSNMR 和 NQR 光谱依赖于与核中心电子势相关的电场梯度 (EFG) 张量的精确计算。虽然 EFG 的静态计算常见于文献中,但对分子和固体中原子动态运动的影响却探讨较少。在本研究中,我们通过基于 DFT 的分子动力学模拟,开发了一种计算固体 EFG 的方法,同时考虑到了原子的动力学。我们开发的方法具有通用性,可以在任何所需的温度和压力下应用于任何材料。在此,我们将重点讨论该方法在 NaNO2 中的应用,并详细研究 14N、17O 和 23Na 的 EFGs。我们发现,在 14N 和 17O 的情况下,原子的动态运动可以用来计算平均 EFG,与静态计算相比,平均 EFG 与实验的吻合度更高。对于 23Na,我们发现当加入原子运动时,EFGs 的行为很复杂,而静态计算根本无法捕捉到这种行为。特别是,我们发现 EFGs 的分布受局部(不断变化的)键环境的影响很大,其模式反映了 23Na 的配位结构。我们希望这里开发的方法能为理解静态 EFG 计算与实验不一致的材料提供一条前进的道路。
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引用次数: 0
Assessing Correlations between Phonon Features and Cation Migration Barriers in Multivalent Solid Electrolytes 评估多价固体电解质中声子特征与阳离子迁移障碍之间的相关性
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-18 DOI: 10.1021/acs.chemmater.4c01468
Samuel M. Greene, Donald J. Siegel
Batteries based on the redox of multivalent cations (Mg2+, Ca2+, Zn2+, Al3+, etc.) offer potential advantages over today’s lithium-ion batteries, but their development is hindered by the sluggish migration of such ions in solid electrodes and electrolytes. Computational screening can accelerate the discovery of more conductive materials, provided that ionic conductivity can be estimated with sufficient accuracy and efficiency. The present study examines whether vibrational properties can be used to predict energetic barriers for cation migration in 24 prototypical multivalent solid electrolytes. Phonon band centers (i.e., mean frequencies), which have been previously used to predict Li-ion conductivity, are calculated using density functional theory. Band centers alone are found not to correlate with migration barriers (R2 = 0.02), perhaps due to poor alignment of low-frequency phonon eigenmodes with ion migration pathways in some materials. A new metric that incorporates both frequencies and alignments─the mean alignment-weighted frequency─is more strongly correlated to migration barriers (R2 = 0.25). Materials in this study with the lowest migration barriers consistently exhibit the lowest mean alignment-weighted frequencies, suggesting the utility of this metric for filtering out materials with high barriers in screening efforts. Comparisons to previous studies suggest that phonon band centers may be correlated to migration barriers only in compositionally similar materials and that adding alignment information may enable more reliable predictions among more diverse sets of materials. These results quantify the promise of using phonon frequencies and alignments, perhaps in combination with other properties, to efficiently screen for materials with high multivalent ionic conductivity.
与当今的锂离子电池相比,基于多价阳离子(Mg2+、Ca2+、Zn2+、Al3+ 等)氧化还原的电池具有潜在的优势,但由于这些离子在固体电极和电解质中的迁移缓慢,其发展受到阻碍。计算筛选可以加速发现导电性更强的材料,但前提是离子电导率的估算必须足够准确和高效。本研究探讨了振动特性是否可用于预测 24 种原型多价固体电解质中阳离子迁移的能量障碍。利用密度泛函理论计算了以前用于预测锂离子电导率的声带中心(即平均频率)。研究发现,仅计算带中心与迁移障碍并不相关(R2 = 0.02),这可能是由于某些材料中低频声子特征模与离子迁移路径的一致性较差。同时包含频率和排列的新指标--平均排列加权频率--与迁移障碍的相关性更强(R2 = 0.25)。在本研究中,迁移障碍最低的材料的平均排列加权频率一直都是最低的,这表明该指标可以在筛选工作中过滤掉障碍较高的材料。与以往研究的比较表明,声子带中心可能只在成分相似的材料中与迁移障碍相关,而添加配准信息可以对更多样化的材料进行更可靠的预测。这些结果量化了利用声子频率和排列(也许与其他特性相结合)有效筛选高多价离子电导率材料的前景。
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引用次数: 0
Tailorable Magnetic Exchange and Optical Absorption in 1-D Double Perovskite-like Halides (CH3NH3)2NaMoCl(6–x)Brx 一维双过氧化物类卤化物 (CH3NH3)2NaMoCl(6-x)Brx 中的可定制磁性交换和光学吸收
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-18 DOI: 10.1021/acs.chemmater.4c00735
Devesh Chandra Binwal, Khyati Anand, Mayank Sharma, Kalluvadi Veetil Saurav, Swapan K. Pati, Pratap Vishnoi
Incorporation of open-shell transition-metal ions in halide double perovskite, A2MIMIIIX6 (where A is a monocation, MI is a monovalent metal, MIII is a trivalent metal, and X is a halide), can lead to the simultaneous emergence of interesting magnetic and optoelectronic properties for various applications. Mixing different halides at the perovskite X-site adds a new direction in tuning the stability and the optical properties. However, their synthesis is often difficult due to complicated compositional evolution and phase segregation. Here, by incorporating a Mo3+ ion (4d3; t2g3eg0) as the magnetic metal in the MIII site and mixing Cl/Br in the X-site, we report four new one-dimensional hybrid double perovskite-like halides: (MA)2NaMoCl(6–x)Brx (MA = CH3NH3+; x = 0.0, 1.17, 2.71 and 4.10). These compounds retain alternate ordering of face-sharing [NaCl(6–x)Brx] and [MoCl(6–x)Brx] polyhedra in infinite one-dimensional chains with the MA cation in the interchain space. We investigate the effect of mixing Cl and Br on optical absorption and magnetic exchange properties using experimental and theoretical methods. Their band gaps are tunable in the 1.98–2.13 eV range, which red shift on increasing the Br content x. The magnetic properties are stimulating. The unpaired electrons of the Mo3+ ion are ordered antiferromagnetically with those of the nearest neighbor Mo3+ ions at transition temperatures in the ∼5.2–6.8 K range. The Curie–Weiss temperature and the transition temperature increase with increasing Br content x due to an enhanced superexchange effect as a consequence of an increase in the covalency of metal–halide bonds. This work presents facile preparation of phase pure hybrid double perovskite-like mixed halides. Their ability to precisely control the chemical composition, optical properties, and magnetic behavior makes them viable candidates as multifunctional materials.
在卤化物双包晶石 A2MIMIIIX6(其中 A 是一价金属,MI 是一价金属,MIII 是三价金属,X 是卤化物)中掺入开壳过渡金属离子,可同时产生有趣的磁性和光电特性,并可用于各种应用。在包晶 X 位上混合不同的卤化物,为调整稳定性和光学特性增添了新的方向。然而,由于复杂的成分演变和相分离,它们的合成通常比较困难。在这里,通过在 MIII 位加入 Mo3+ 离子 (4d3; t2g3eg0) 作为磁性金属,并在 X 位混合 Cl/Br,我们报告了四种新的一维混合双包晶类卤化物:(MA)2NaMoCl(6-x)Brx(MA = CH3NH3+;x = 0.0、1.17、2.71 和 4.10)。这些化合物在无限的一维链中保留了面共享[NaCl(6-x)Brx]和[MoCl(6-x)Brx]多面体的交替排序,MA 阳离子位于链间空间。我们利用实验和理论方法研究了 Cl 和 Br 混合对光吸收和磁交换特性的影响。它们的带隙在 1.98-2.13 eV 范围内可调,并随着 Br 含量 x 的增加而发生红移。在 5.2-6.8 K 的转变温度范围内,Mo3+ 离子的未成对电子与近邻 Mo3+ 离子的未成对电子呈反铁磁性有序排列。居里-韦斯温度和转变温度随 Br 含量 x 的增加而升高,这是由于金属-卤化物键的共价性增加导致超交换效应增强。本研究提出了一种相纯混合双包晶类混合卤化物的简便制备方法。这种混合卤化物能够精确控制化学成分、光学性质和磁学行为,因此是一种可行的多功能材料。
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引用次数: 0
New Plastic Crystal Composite Electrodes Employing Delocalized Transition Metal Salts for Low-Cost, High-Safety All-Solid-State Salt Batteries 低成本、高安全性全固态盐电池所需的新型塑料晶体复合电极,采用了失焦过渡金属盐
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-17 DOI: 10.1021/acs.chemmater.4c01003
Yan Liang, Robert Kerr, Xiaoen Wang, Hiroyuki Ueda, Michel Armand, Maria Forsyth, Patrick C. Howlett
We demonstrate a novel approach to creating soft interphases that can comprise both the cathode and electrolyte structures for advanced all-solid-state Li ion batteries. Organic ionic plastic crystals (OIPCs) with promising properties, such as soft and plastic texture, nonflammability, high electrochemical, thermal stability, and high ion conductivity, were employed in both the cathode and solid-state electrolyte (SSE). By incorporating a delocalized transition metal salt active material (exemplified by Fe(BF4)2·6H2O in this work) and graphene, the OIPC composite provides high ion conductivity to the electrode and forms a new phase that supports redox activity when doped with Li or Na salts. The 2.8 V OIPC-Fe(BF4)2·6H2O|Li solid-state battery achieves an initial discharge capacity of 150.6 mAh g–1 at 0.05C and 50 °C, retaining 78 mAh g–1 after 50 cycles. The rate performance of the OIPC electrode is superior to that of an equivalent cathode using a commercial CMC binder, highlighting the role of the OIPC in enhancing the Fe(BF4)2·6H2O utilization. This approach has also been extended to Na-based batteries as a proof of concept, demonstrating stable cycling with an average discharge capacity of 102 mAh g–1 at 0.1C and 50 °C for over 100 cycles. This discovery opens opportunities to explore the vast scope of OIPC and salt design to create new low-cost and safe solid-state batteries.
我们展示了一种新型方法,可为先进的全固态锂离子电池制造阴极和电解质结构的软质相间体。我们在阴极和固态电解质(SSE)中都采用了有机离子塑料晶体(OIPCs),这种晶体具有良好的特性,例如质地柔软、可塑性强、不易燃、电化学和热稳定性高以及离子导电率高。通过将局部过渡金属盐活性材料(本研究中以 Fe(BF4)2-6H2O 为例)和石墨烯结合在一起,OIPC 复合材料为电极提供了高离子传导性,并在掺杂锂盐或钠盐时形成了支持氧化还原活性的新相。2.8 V OIPC-Fe(BF4)2-6H2O|Li 固态电池在 0.05C 和 50 °C 下的初始放电容量为 150.6 mAh g-1,循环 50 次后仍能保持 78 mAh g-1。OIPC 电极的速率性能优于使用商用 CMC 粘合剂的等效阴极,凸显了 OIPC 在提高 Fe(BF4)2-6H2O 利用率方面的作用。作为概念验证,这种方法还被推广到钠基电池上,在 0.1C 和 50°C 温度条件下,经过 100 多个循环后,显示出稳定的循环能力,平均放电容量为 102 mAh g-1。这一发现为探索 OIPC 和盐设计的广阔前景提供了机会,从而创造出新的低成本、安全的固态电池。
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引用次数: 0
Noncentrosymmetric Nowotny Chimney Ladder Ferromagnet Cr4Ge7 with a High Curie Temperature of ∼207 K 居里温度高达 ∼207 K 的非五次对称诺沃特尼烟囱梯形铁磁体 Cr4Ge7
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-16 DOI: 10.1021/acs.chemmater.4c00669
Zhenhai Yu, Kaijuan Zhou, Xiaofei Hou, Xuejiao Chen, Zhen Tao, Yunguan Ye, Wei Xia, Zhongyang Li, Jinggeng Zhao, Wei Wu, Ziyi Liu, Xia Wang, Na Yu, Jinguang Cheng, Jian-Lin Luo, Qiang Zhang, Vladimir Y. Pomjakushin, Zhicheng Zhong, Shihao Zhang, Jian-Rui Soh, Xingye Lu, Yanfeng Guo
Noncentrosymmetric magnets usually host intriguing magnetic interactions inherent in the crystal structure with broken inversion symmetry, which can give rise to rich magnetic behaviors. We report herein the high-pressure synthesis, crystal structure, magnetizations, and magnetic structure of a so-called Nowotny chimney ladder compound Cr4Ge7. Our analysis on the powder neutron diffraction data revises the crystal structure as a noncentrosymmetric space group (Pc2, No. 116). It exhibits two magnetic orders within the temperature range of 2–400 K. The first order at ∼207 K associated with a small magnetic moment of ∼0.75 μB is assigned to a commensurate ferromagnetic structure with a propagation vector k = (0, 0, 0). The weak itinerant ferromagnet nature should be caused by the complex Cr spin orders from different Wyckoff positions. The second order-like behavior at ∼18 K is assumed to arise from a competition between the Dzyaloshinskii–Moriya and Heisenberg interactions. The results provide an excellent platform for the study of intricate interactions among various magnetic exchanges as well as for the exploration of high-temperature exotic magnetic properties.
非五次对称磁体通常在晶体结构中存在固有的有趣的磁相互作用,其反转对称性被打破,从而产生丰富的磁性行为。我们在此报告了所谓的诺沃特尼烟囱梯形化合物 Cr4Ge7 的高压合成、晶体结构、磁化和磁结构。我们对粉末中子衍射数据的分析将晶体结构修正为非五次对称空间群(P4̅c2,No.116)。它在 2-400 K 的温度范围内显示出两个磁阶。在 ∼207 K 的第一个磁阶与 ∼0.75 μB 的小磁矩有关,它被归结为具有传播矢量 k = (0, 0, 0) 的相称铁磁结构。弱巡回铁磁体性质应该是由来自不同 Wyckoff 位置的复杂 Cr 自旋阶造成的。假设在 ∼18 K 时的二阶行为来自 Dzyaloshinskii-Moriya 和 Heisenberg 相互作用之间的竞争。这些结果为研究各种磁交换之间错综复杂的相互作用以及探索高温奇异磁性能提供了一个极好的平台。
{"title":"Noncentrosymmetric Nowotny Chimney Ladder Ferromagnet Cr4Ge7 with a High Curie Temperature of ∼207 K","authors":"Zhenhai Yu, Kaijuan Zhou, Xiaofei Hou, Xuejiao Chen, Zhen Tao, Yunguan Ye, Wei Xia, Zhongyang Li, Jinggeng Zhao, Wei Wu, Ziyi Liu, Xia Wang, Na Yu, Jinguang Cheng, Jian-Lin Luo, Qiang Zhang, Vladimir Y. Pomjakushin, Zhicheng Zhong, Shihao Zhang, Jian-Rui Soh, Xingye Lu, Yanfeng Guo","doi":"10.1021/acs.chemmater.4c00669","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c00669","url":null,"abstract":"Noncentrosymmetric magnets usually host intriguing magnetic interactions inherent in the crystal structure with broken inversion symmetry, which can give rise to rich magnetic behaviors. We report herein the high-pressure synthesis, crystal structure, magnetizations, and magnetic structure of a so-called Nowotny chimney ladder compound Cr<sub>4</sub>Ge<sub>7</sub>. Our analysis on the powder neutron diffraction data revises the crystal structure as a noncentrosymmetric space group (<i>P</i>4̅<i>c</i>2, No. 116). It exhibits two magnetic orders within the temperature range of 2–400 K. The first order at ∼207 K associated with a small magnetic moment of ∼0.75 μ<sub>B</sub> is assigned to a commensurate ferromagnetic structure with a propagation vector <i><b>k</b></i> = (0, 0, 0). The weak itinerant ferromagnet nature should be caused by the complex Cr spin orders from different Wyckoff positions. The second order-like behavior at ∼18 K is assumed to arise from a competition between the Dzyaloshinskii–Moriya and Heisenberg interactions. The results provide an excellent platform for the study of intricate interactions among various magnetic exchanges as well as for the exploration of high-temperature exotic magnetic properties.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141625161","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Bulky Ligands Induce Rich Uncoordinated Sites for Boosting Metal Nanocluster Catalysis 大块配体诱导丰富的非配位位点,促进金属纳米簇催化反应
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-16 DOI: 10.1021/acs.chemmater.4c01046
Huifang Guo, Yuping Chen, Ying-Zi Han, Qingyuan Wu, Lin Wang, Qinghua Xu, Rong Huo, Xuekun Gong, Jing Sun, Qing Tang, Hui Shen
The catalytic activity of ligand-protected metal nanoclusters is often hindered by the blocking effect of surface ligands, necessitating the creation of more uncoordinated sites to enhance their performance. In this work, we report a strategy for boosting the catalysis of fully ligand-protected silver nanoclusters by anchoring uncoordinated copper sites. By employing a bulky ligand, 2,4,6-triisopropylbenzenethiol, and a copper-functionalized reducing agent, a cluster denoted as Ag14Cu7(PPh3)6(SR)6 (Ag14Cu7, RSH is 2,4,6-triisopropylbenzenethiol) has been prepared. The structure of Ag14Cu7 closely resembles that of the previously reported Ag14(SPh(CF3)2)12(PPh3)4(DMF)4 (Ag14), whose geometric structure describes the addition of seven Cu atoms onto the Ag14 moiety, one at the center and another six on the surface. To our surprise, the presence of extra uncoordinated copper sites on the surface significantly enhances the catalytic activity of Ag14Cu7 in hydrogenation reactions. This work not only reports a model system to shed light on the significance of surface uncoordinated metal sites in cluster catalysis but also offers an effective strategy utilizing bulky ligands and functionalized reducing agents to generate additional uncoordinated sites on the surface of metal nanocluster catalysts.
受配体保护的金属纳米簇的催化活性通常会受到表面配体阻滞效应的阻碍,因此需要创造更多的非配位位点来提高其性能。在这项工作中,我们报告了一种通过锚定非配位铜位点来增强完全配体保护的银纳米簇催化作用的策略。通过使用笨重的配体(2,4,6-三异丙基苯硫酚)和铜官能还原剂,我们制备出了名为 Ag14Cu7(PPh3)6(SR)6(Ag14Cu7,RSH 为 2,4,6-三异丙基苯硫酚)的团簇。Ag14Cu7 的结构与之前报道的 Ag14(SPh(CF3)2)12(PPh3)4(DMF)4) (Ag14)非常相似,其几何结构描述了在 Ag14 分子上添加了七个铜原子,一个位于中心,另外六个位于表面。令我们惊讶的是,表面额外非配位铜位点的存在大大提高了 Ag14Cu7 在氢化反应中的催化活性。这项工作不仅报告了一个模型体系,揭示了表面非配位金属位点在簇催化中的重要意义,还提供了一种有效的策略,即利用笨重配体和功能化还原剂在金属纳米簇催化剂表面生成额外的非配位位点。
{"title":"Bulky Ligands Induce Rich Uncoordinated Sites for Boosting Metal Nanocluster Catalysis","authors":"Huifang Guo, Yuping Chen, Ying-Zi Han, Qingyuan Wu, Lin Wang, Qinghua Xu, Rong Huo, Xuekun Gong, Jing Sun, Qing Tang, Hui Shen","doi":"10.1021/acs.chemmater.4c01046","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01046","url":null,"abstract":"The catalytic activity of ligand-protected metal nanoclusters is often hindered by the blocking effect of surface ligands, necessitating the creation of more uncoordinated sites to enhance their performance. In this work, we report a strategy for boosting the catalysis of fully ligand-protected silver nanoclusters by anchoring uncoordinated copper sites. By employing a bulky ligand, 2,4,6-triisopropylbenzenethiol, and a copper-functionalized reducing agent, a cluster denoted as Ag<sub>14</sub>Cu<sub>7</sub>(PPh<sub>3</sub>)<sub>6</sub>(SR)<sub>6</sub> (Ag<sub>14</sub>Cu<sub>7</sub>, RSH is 2,4,6-triisopropylbenzenethiol) has been prepared. The structure of Ag<sub>14</sub>Cu<sub>7</sub> closely resembles that of the previously reported Ag<sub>14</sub>(SPh(CF<sub>3</sub>)<sub>2</sub>)<sub>12</sub>(PPh<sub>3</sub>)<sub>4</sub>(DMF)<sub>4</sub> (Ag<sub>14</sub>), whose geometric structure describes the addition of seven Cu atoms onto the Ag<sub>14</sub> moiety, one at the center and another six on the surface. To our surprise, the presence of extra uncoordinated copper sites on the surface significantly enhances the catalytic activity of Ag<sub>14</sub>Cu<sub>7</sub> in hydrogenation reactions. This work not only reports a model system to shed light on the significance of surface uncoordinated metal sites in cluster catalysis but also offers an effective strategy utilizing bulky ligands and functionalized reducing agents to generate additional uncoordinated sites on the surface of metal nanocluster catalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141625187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Expanding the Family of Magnetic Vacancy-Ordered Halide Double Perovskites 扩展磁空位有序卤化物双包晶家族
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-16 DOI: 10.1021/acs.chemmater.4c01880
Kurt P. Lindquist, Teresa Lee, Xianghan Xu, Robert J. Cava
Vacancy-ordered halide double perovskites, with the general formula A2IBIVX6, can accommodate a wide variety of tetravalent B-site cations. However, few examples containing trivalent B-site cations exist, limiting the variety of magnetic cations that can comprise this structure type. Here, we incorporate divalent A-site cations to form the vacancy-ordered double perovskites AIAIIBIIICl6 (AI = Na, K, Rb, Cs; AII = Sr, Ba; BIII = Ti, V, Cr, Ir) and Ba1.5BIIICl6 (BIII = V, Cr). By tuning the radius of the A-site through cation substitution, we form four structure-types with these formulas, including a K2PtCl6-type structure, a low-temperature K2SnCl6-type structure, a novel derivative with ordered A1+/A2+ cations, and a second novel derivative with ordered A-site vacancies. This structural diversity, which includes 22 unique compositions, allows us to study the effect of structure and composition on the magnetic properties of these solids, which show antiferromagnetic coupling of weak-to-moderate strength and signatures of frustrated long-range ordering. Furthermore, our studies of temperature-dependent magnetism and heat capacity reveal that the magnetic coupling strength decreases with octahedral tilting, consistent with expectations; in contrast, the coupling strength counterintuitively increases from BIII = Ti to Cr to V, which we speculate may be a result of competing antiferromagnetic and ferromagnetic interactions. By substituting divalent A-site cations into vacancy-ordered halide double perovskites, we further expand the already rich phase space of these structures to include magnetic trivalent transition metals and deepen our understanding of structure–magnetism relationships in metal halides.
通式为 A2IBIVX6 的空位有序卤化物双包晶石可容纳多种四价 B 位阳离子。然而,含有三价 B 位阳离子的例子很少,这限制了这种结构类型的磁性阳离子的多样性。在这里,我们加入了二价 A 位阳离子,形成了空位有序双包晶 AIAIIBIIICl6(AI = Na、K、Rb、Cs;AII = Sr、Ba;BIII = Ti、V、Cr、Ir)和 Ba1.5BIIICl6(BIII = V、Cr)。通过阳离子置换调整 A 位半径,我们利用这些公式形成了四种结构类型,包括 K2PtCl6 型结构、低温 K2SnCl6 型结构、具有有序 A1+/A2+ 阳离子的新型衍生物以及具有有序 A 位空位的第二种新型衍生物。这种结构多样性(包括 22 种独特成分)使我们能够研究结构和成分对这些固体磁性能的影响,它们显示出弱到中等强度的反铁磁耦合和受挫长程有序的特征。此外,我们对随温度变化的磁性和热容量的研究表明,磁性耦合强度随八面体倾斜而减小,这与预期一致;相反,从 BIII = Ti 到 Cr 再到 V,耦合强度反常地增大,我们推测这可能是反铁磁性和铁磁性相互作用竞争的结果。通过将二价 A 位阳离子置换到空位有序的卤化物双包晶中,我们进一步拓展了这些结构本已丰富的相空间,将具有磁性的三价过渡金属也纳入其中,加深了我们对金属卤化物结构-磁性关系的理解。
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引用次数: 0
Investigating the Effects of Hydrogen Bonding on Mechanical and Electrical Properties of n-Type Semicrystalline Polymers 研究氢键对 n 型半结晶聚合物机械和电气性能的影响
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-16 DOI: 10.1021/acs.chemmater.4c01516
Soodeok Seo, Qingpei Wan, Eun Sung Oh, Steven M. Sheppard, Jin-Woo Lee, Chulhee Lim, Taek-Soo Kim, Barry C. Thompson, Bumjoon J. Kim
Designing conjugated polymers with both excellent electrical properties and mechanical robustness is a prerequisite for their application in wearable and portable electronics. However, many of the efficient conjugated polymers are mechanically brittle due to their strong semicrystallinity, and only the limited amorphous parts contribute to the overall tensile properties. Here, we have incorporated monomers with hydrogen bonding (H-bonding) functionalized side chains (Qx-thymine and T-diaminopyrimidine) into the backbone of the naphthalene diimide-based semicrystalline polymer, N2200, to yield electroactive polymers with high electrical properties and stretchability, facilitated by dynamic bonding-assisted intermolecular assembly. To elucidate the impact of H-bonding on polymer properties, we systematically compare the mechanical and electrical properties, among the reference N2200 polymer, N2200-based terpolymers (Qx10 and Ester10) having side chains without H-bonding, and N2200-based terpolymers (Thy10 and Dap10) having QX-thymine and T-diaminopyrimidine side chains. Interestingly, introducing H-bonding units into polymers promotes the formation of intermolecular assembly while reducing the critical molecular weight (Mc) of the polymer chain, thus facilitating the formation of tie-molecules and entanglement networks. Specifically, Thy10 polymers, with a weight-average molecular weight (Mw) of 133 kg mol–1, achieve a significantly higher stretchability with crack-onset strain (COS) = 49.3% compared to those of the N2200 (Mw = 180 kg mol–1, COS= 3.2%) and Qx10 polymers (Mw = 144 kg mol–1, COS = 23.7%) with comparable Mw. Furthermore, Thy10 exhibits superior crystalline properties and more efficient charge transport compared with Qx10, highlighting the utility of H-bonding-capable conjugated polymers in wearable electronics.
设计出兼具出色电气性能和机械坚固性的共轭聚合物,是将其应用于可穿戴和便携式电子产品的先决条件。然而,许多高效共轭聚合物由于具有很强的半结晶性而在机械性能上比较脆,只有有限的无定形部分对整体拉伸性能有所贡献。在这里,我们将具有氢键(H-bonding)功能化侧链(Qx-胸腺嘧啶和 T-二氨基嘧啶)的单体加入到萘二亚胺基半结晶聚合物 N2200 的骨架中,通过动态键合辅助分子间组装,得到了具有高电性能和可拉伸性的电活性聚合物。为了阐明 H 键对聚合物性能的影响,我们系统地比较了参考 N2200 聚合物、具有无 H 键侧链的 N2200 基三元共聚物(Qx10 和 Ester10)以及具有 QX-胸腺嘧啶和 T-二氨基嘧啶侧链的 N2200 基三元共聚物(Thy10 和 Dap10)的机械和电气性能。有趣的是,在聚合物中引入 H 键单元可促进分子间组装的形成,同时降低聚合物链的临界分子量(Mc),从而促进连接分子和纠缠网络的形成。具体来说,Thy10 聚合物的重量平均分子量(Mw)为 133 千克摩尔-1,与具有类似 Mw 的 N2200 聚合物(Mw=180 千克摩尔-1,COS=3.2%)和 Qx10 聚合物(Mw=144 千克摩尔-1,COS=23.7%)相比,Thy10 聚合物的伸展性显著提高,裂纹发生应变(COS)=49.3%。此外,与 Qx10 相比,Thy10 表现出更优越的结晶特性和更高效的电荷传输,突出了具有 H 键能力的共轭聚合物在可穿戴电子设备中的应用。
{"title":"Investigating the Effects of Hydrogen Bonding on Mechanical and Electrical Properties of n-Type Semicrystalline Polymers","authors":"Soodeok Seo, Qingpei Wan, Eun Sung Oh, Steven M. Sheppard, Jin-Woo Lee, Chulhee Lim, Taek-Soo Kim, Barry C. Thompson, Bumjoon J. Kim","doi":"10.1021/acs.chemmater.4c01516","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01516","url":null,"abstract":"Designing conjugated polymers with both excellent electrical properties and mechanical robustness is a prerequisite for their application in wearable and portable electronics. However, many of the efficient conjugated polymers are mechanically brittle due to their strong semicrystallinity, and only the limited amorphous parts contribute to the overall tensile properties. Here, we have incorporated monomers with hydrogen bonding (H-bonding) functionalized side chains (Qx-thymine and T-diaminopyrimidine) into the backbone of the naphthalene diimide-based semicrystalline polymer, N2200, to yield electroactive polymers with high electrical properties and stretchability, facilitated by dynamic bonding-assisted intermolecular assembly. To elucidate the impact of H-bonding on polymer properties, we systematically compare the mechanical and electrical properties, among the reference N2200 polymer, N2200-based terpolymers (Qx10 and Ester10) having side chains without H-bonding, and N2200-based terpolymers (Thy10 and Dap10) having Q<sub>X</sub>-thymine and T-diaminopyrimidine side chains. Interestingly, introducing H-bonding units into polymers promotes the formation of intermolecular assembly while reducing the critical molecular weight (<i>M</i><sub>c</sub>) of the polymer chain, thus facilitating the formation of tie-molecules and entanglement networks. Specifically, Thy10 polymers, with a weight-average molecular weight (<i>M</i><sub>w</sub>) of 133 kg mol<sup>–1</sup>, achieve a significantly higher stretchability with crack-onset strain (COS) = 49.3% compared to those of the N2200 (<i>M</i><sub>w</sub> = 180 kg mol<sup>–1</sup>, COS= 3.2%) and Qx10 polymers (<i>M</i><sub>w</sub> = 144 kg mol<sup>–1</sup>, COS = 23.7%) with comparable <i>M</i><sub>w</sub>. Furthermore, Thy10 exhibits superior crystalline properties and more efficient charge transport compared with Qx10, highlighting the utility of H-bonding-capable conjugated polymers in wearable electronics.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141631726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
How to Enhance Anomalous Hall Effects in Magnetic Weyl Semimetal Co3Sn2S2? 如何增强磁性韦尔半金属 Co3Sn2S2 中的反常霍尔效应?
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-15 DOI: 10.1021/acs.chemmater.4c01384
Shivam Rathod, Megha Malasi, Archana Lakhani, Devendra Kumar
Large spin–orbit coupling, kagome lattice, nontrivial topological band structure with inverted bands anticrossings, and Weyl nodes are essential ingredients ideally required to obtain maximal anomalous Hall effect (AHE) and are all present in Co3Sn2S2. It is a leading platform to show large intrinsic anomalous Hall conductivity (AHC) and giant anomalous Hall angle (AHA) simultaneously at low fields. The giant AHE in Co3Sn2S2 is robust against small-scale doping-related chemical potential changes. In this work, we unveil a selective and cochemical doping route to maximize AHEs in Co3Sn2S2. To begin with, in Co3Sn2–xInxS2, we brought the chemical potential at the hot spot of Berry curvature along with a maximum of asymmetric impurity scattering in the high mobility region. As a result, at x = 0.05, we found a significant enhancement of the AHA (95%) and AHC (190%) from the synergistic enhancement of extrinsic and intrinsic mechanisms due to the modified Berry curvature of gapped nodal lines. Later, with anticipation of further improvements in the AHE, we grew hole-co-doped Co3–yFeySn2–xInxS2 crystals, where we surprisingly found a suppression of AHEs. The role of dopants in giving extrinsic effects or band broadening can be better understood if the chemical potential does not change on doping. By simultaneous and equal codoping with electrons and holes in Co3–yzFeyNizSn2S2, we kept the chemical potential unchanged. Henceforth, we found a significant enhancement in intrinsic AHC of ∼ 116% due to the disorder broadening in the kagome bands.
大自旋轨道耦合、卡戈米晶格、具有倒带反交的非难拓扑带状结构以及韦尔节点是获得最大反常霍尔效应(AHE)的理想条件,而这些要素在 Co3Sn2S2 中全部存在。Co3Sn2S2 是一个领先的平台,可在低磁场下同时显示大的本征反常霍尔电导率(AHC)和巨型反常霍尔角(AHA)。Co3Sn2S2 中的巨反常霍尔电导不受小尺度掺杂相关化学势变化的影响。在这项工作中,我们揭示了一条选择性共化学掺杂路线,以最大限度地提高 Co3Sn2S2 中的 AHE。首先,在 Co3Sn2-xInxS2 中,我们使贝里曲率热点处的化学势与高迁移率区域的非对称杂质散射达到最大值。结果,在 x = 0.05 时,我们发现由于间隙结线的贝里曲率改变,外在和内在机制协同增强,AHA(95%)和 AHC(190%)显著提高。后来,为了进一步改善 AHE,我们生长了掺杂空穴的 Co3-yFeySn2-xInxS2 晶体,结果出人意料地发现 AHE 受到了抑制。如果掺杂时化学势不发生变化,就能更好地理解掺杂剂在产生外效应或带宽方面的作用。通过在 Co3-yzFeyNizSn2S2 中同时等量掺入电子和空穴,我们保持了化学势不变。因此,我们发现由于 kagome 带的无序展宽,本征 AHC 显著增强了 116%。
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引用次数: 0
Methods for Preparation of Hexagonal Boron Nitride Nanomaterials 六方氮化硼纳米材料的制备方法
IF 8.6 2区 材料科学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2024-07-15 DOI: 10.1021/acs.chemmater.4c00582
Dehong Yang, Pengcheng Dai, Xiangfen Jiang, Saad M. Alshehri, Tansir Ahamad, Yoshio Bando, Xuebin Wang
Hexagonal boron nitride (h-BN) represents a promising inorganic compound, garnering widespread attention for its unique combination of electrical insulation, thermal conductivity, lightweight nature, and chemical stability. The past decades have witnessed the advent of diverse h-BN nanostructures, which preserve the intrinsic superior attributes of h-BN while endowing these materials with unique nanoscale properties. This paper aims to provide a comprehensive review of the synthesis methods for h-BN nanomaterials across different dimensions. Furthermore, it outlines the applications of h-BN nanomaterials in energy storage, thermal management, catalysis, and other fields, and concludes with a discussion of challenges and prospects. It is conceived as a foundational guide aimed at the practical production of h-BN nanomaterials.
六方氮化硼(h-BN)是一种前景广阔的无机化合物,因其独特的绝缘性、导热性、轻质性和化学稳定性而受到广泛关注。在过去的几十年中,出现了多种多样的 h-BN 纳米结构,它们在保持 h-BN 固有优越性能的同时,还赋予了这些材料独特的纳米级特性。本文旨在全面综述不同尺寸 h-BN 纳米材料的合成方法。此外,本文还概述了 h-BN 纳米材料在储能、热管理、催化等领域的应用,并在最后讨论了其面临的挑战和发展前景。该书旨在为 h-BN 纳米材料的实际生产提供基础性指导。
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引用次数: 0
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Chemistry of Materials
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