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Cryoprotective Polyol-Induced Ice Microstructure Development and Enhanced Chromium(VI) Reduction in Polycrystalline Structures 低温保护多元醇诱导多晶体结构中冰微观结构的发展和铬(VI)还原能力的增强
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-28 DOI: 10.1021/acs.cgd.4c0106710.1021/acs.cgd.4c01067
Bomi Kim,  and , Kitae Kim*, 

Cryoprotective polyols play a crucial role in inhibiting ice crystal growth, reducing the size of bulk ice crystals in polycrystalline structures, and increasing the volume of ice grain boundaries relative to the total solution volume. This study suggests that these properties enable cryoprotective polyols to accelerate the reduction of hexavalent chromium (Cr(VI)) in ice despite the reducing agents being limited to aqueous environments. This reaction is mainly caused by the accumulation of cryoprotective polyols and Cr(VI) at the ice grain boundaries formed during freezing (i.e., the freeze concentration effect). Upon freezing a mixture of cryoprotective polyols and a 20 μM Cr(VI) solution, over 90% reduction in Cr(VI) concentration was achieved within 24 h. Higher concentrations of cryoprotective polyols in Cr(VI) enhanced the reduction kinetics of Cr(VI) over the same reaction time, implying that the cryoprotective polyols function as reducing agents under freezing conditions. Confocal Raman spectroscopy confirmed cryoprotective polyols bind to ice crystal surfaces and concentrate Cr(VI) at the ice grain boundaries. Notably, the reductive capability of cryoprotective polyols toward Cr(VI) was observed under freezing conditions, using an electroplating wastewater sample contaminated with Cr(VI) as a model system, whereas negligible reduction was observed in the aqueous phase. Enhanced Cr(VI) reduction by cryoprotective polyols in frozen solutions presents a viable approach for treating contaminated wastewater and contributes to understanding the self-purification mechanism in natural environments where these polyols are present.

低温保护多元醇在抑制冰晶生长、减小多晶结构中块状冰晶的大小以及增加冰晶边界体积(相对于溶液总体积)方面发挥着至关重要的作用。本研究表明,尽管还原剂仅限于水环境,但这些特性使低温保护多元醇能够加速冰中六价铬(Cr(VI))的还原。造成这种反应的主要原因是冷冻保护多元醇和六价铬在冷冻过程中形成的冰晶界处的积聚(即冷冻浓缩效应)。冷冻保护性多元醇和 20 μM 六价铬溶液的混合物时,六价铬浓度在 24 小时内降低了 90%以上。在相同的反应时间内,六价铬中较高浓度的冷冻保护性多元醇提高了六价铬的降低动力学,这意味着冷冻保护性多元醇在冷冻条件下起到了还原剂的作用。共焦拉曼光谱证实,低温保护多元醇与冰晶表面结合,并在冰晶边界浓缩六价铬。值得注意的是,以受六价铬污染的电镀废水样品为模型系统,在冷冻条件下观察到了低温保护多元醇对六价铬的还原能力,而在水相中观察到的还原能力微乎其微。低温保护多元醇在冷冻溶液中增强的六(Cr)还原能力为处理受污染的废水提供了一种可行的方法,并有助于了解存在这些多元醇的自然环境中的自净机制。
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引用次数: 0
Methane Hydrates Formed in a Porous Graphene Aerogel for Energy Storage 多孔石墨烯气凝胶中形成的甲烷水合物用于储能
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-25 DOI: 10.1021/acs.cgd.4c0122010.1021/acs.cgd.4c01220
Xiaoming Wang, Li Li, Yan Lin, Jin Xu, Jiatao Zhao, Xiaoguang Zhang*, Fei Wang* and Xiaolin Wang, 

The use of porous media as a fixed bed for promoting methane hydrate formation has been endowed with great potential in hydrate-based energy storage. In this work, a graphene aerogel (GA) with a one-piece structure and ultralight weight was prepared and adopted for the first time as a fixed bed for methane hydrate formation. In particular, the effects of the filling ratio and hydrophobic–hydrophilic properties of GA on the promotion efficiency were comprehensively investigated. In the range of 84–95%, a lower filling ratio resulted in higher promotion efficiency, which at 84% increased the methane storage capacity and apparent storage capacity from 114.4 ± 7.6 and 52.4 ± 6.7 V/V to 146.3 ± 6.5 and 91.1 ± 13.0 V/V, respectively. Cryo-scanning electron microscopy (Cryo-SEM) demonstrated that the hydrates formed in the inner pores of GA but also revealed the existence of empty pores, indicating that part of the reaction solution migrated out of the GA. Fortunately, by regulating the hydrophilic–hydrophobic properties of GA, the migration of the reaction solution during hydrate growth could be controlled, and the methane storage capacity could be optimized. More importantly, GA produced excellent advantages in terms of gravimetric storage capacity over traditional media and, therefore, produced great potential in serving as an ultralight fixed bed for the industrial application of hydrate-based energy storage.

将多孔介质用作促进甲烷水合物形成的固定床在基于水合物的能源储存方面具有巨大潜力。本研究首次制备并采用了具有一体式结构和超轻重量的石墨烯气凝胶(GA)作为甲烷水合物形成的固定床。特别是全面研究了石墨烯气凝胶的填充率和疏水亲水特性对促进效率的影响。在 84-95% 的范围内,填充率越低,促进效率越高,当填充率为 84% 时,甲烷储存量和表观储存量分别从 114.4 ± 7.6 和 52.4 ± 6.7 V/V 提高到 146.3 ± 6.5 和 91.1 ± 13.0 V/V。低温扫描电子显微镜(Cryo-SEM)显示,水合物形成于 GA 的内孔,但同时也发现了空孔的存在,表明部分反应溶液从 GA 中迁移出来。幸运的是,通过调节 GA 的亲水疏水特性,可以控制水合物生长过程中反应溶液的迁移,从而优化甲烷的储存能力。更重要的是,与传统介质相比,GA 在重力储存能力方面具有卓越的优势,因此在作为超轻固定床用于水合物储能的工业应用方面具有巨大潜力。
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引用次数: 0
Polymer–Mineral Interaction Influences the Mineralization of Hydroxyapatite in Hydrogels 聚合物-矿物相互作用影响水凝胶中羟基磷灰石的矿化
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-25 DOI: 10.1021/acs.cgd.4c0100210.1021/acs.cgd.4c01002
Yongjian Ma, Jiheon Kwon, Rui Ji and Rosa M. Espinosa-Marzal*, 

Bone mineralization relies on the interaction between collagen and minerals to control bone growth and multiscale hierarchical structure. Urged by the increasing need for bone defect repairs, tissue engineering searches for biocompatible materials to assist and enhance repairs. One potential avenue is to use hydrogels as organic scaffolds to control nucleation and growth of bonelike minerals. Here, two biocompatible polymers, polyacrylamide and agarose, were selected for the mineralization of hydroxyapatite, and the mineralization kinetics was investigated in the presence of calcium carbonate (to simulate early bone formation conditions) and in its absence. The results of this work show that agarose and polyacrylamide lead to different polymer–mineral interactions, which influence the stabilization of carbonate and phosphate precursors and thereby the onset of the crystallization of hydroxyapatite and more so in the presence of carbonate. In both hydrogels, amorphous calcium carbonate and hydroxyapatite are noncongruent, and amorphous calcium phosphate forms as a precursor. This distinct interaction between the mineral and agarose vs polyacrylamide leads to different microstructures and thereby mechanical responses. This research not only advances our understanding of the influence of mineral–polymer interactions on hydroxyapatite mineralization but also provides new opportunities for designing biomaterials for specific applications.

骨骼矿化依靠胶原蛋白和矿物质之间的相互作用来控制骨骼生长和多尺度分层结构。在骨缺损修复需求日益增长的推动下,组织工程学正在寻找生物相容性材料来辅助和加强修复。一个潜在的途径是使用水凝胶作为有机支架来控制类骨矿物质的成核和生长。在这里,我们选择了聚丙烯酰胺和琼脂糖这两种生物相容性聚合物用于羟基磷灰石的矿化,并研究了在碳酸钙存在(模拟早期骨骼形成条件)和不存在碳酸钙时的矿化动力学。这项工作的结果表明,琼脂糖和聚丙烯酰胺会导致不同的聚合物-矿物质相互作用,从而影响碳酸盐和磷酸盐前体的稳定,进而影响羟基磷灰石结晶的开始,在有碳酸盐存在的情况下影响更大。在这两种水凝胶中,无定形碳酸钙和羟基磷灰石是不协调的,无定形磷酸钙作为前体形成。矿物与琼脂糖和聚丙烯酰胺之间的这种不同相互作用导致了不同的微观结构,从而产生了不同的机械反应。这项研究不仅加深了我们对矿物-聚合物相互作用对羟基磷灰石矿化的影响的理解,还为设计特定应用的生物材料提供了新的机遇。
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引用次数: 0
New Insights into the Structure, Thermal Properties, and Photostability of Industrially Relevant Salts of Sorbic Acid 对山梨酸工业相关盐类的结构、热性能和光稳定性的新认识
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-24 DOI: 10.1021/acs.cgd.4c0119710.1021/acs.cgd.4c01197
Paulina Kalle*, Stanislav I. Bezzubov, Lyudmila G. Kuzmina and Andrei V. Churakov, 

Potassium, sodium, and calcium salts of sorbic acid (CH3–CH═CH–CH═CH–COOH) are widely used food preservatives. Despite the industrial relevance, their solid-state chemistry associated with photoreactivity and heat-induced transformations of double bonds remains misunderstood, mostly because of the lack of structural information. Herein, we report a comprehensive structural, thermal, and spectroscopic study of the above sorbates along with previously unknown normal and acid ammonium sorbates for comparison. Although all of the crystal structures exhibit a similar layered motif and carboxylate coordination, in potassium sorbate, there is an additional noncovalent interaction between K+ and the Cα═Cβ bond that bestows the salt with unique thermal properties. In turn, only the acid ammonium sorbate has a preorganization for [2 + 2] photocycloaddition, as reflected by its fast amorphization under soft UV irradiation, opposite to the other salts. The experimental results are discussed in the context of related metal carboxylates and the application and analysis of the studied salts in food industry.

山梨酸(CH3-CH═CH-CH═CH-COOH)的钾盐、钠盐和钙盐是广泛使用的食品防腐剂。尽管与工业密切相关,但它们与光活性和热诱导双键转化有关的固态化学性质仍被误解,这主要是因为缺乏结构信息。在此,我们报告了对上述山梨酸盐以及之前未知的普通山梨酸铵和酸性山梨酸铵进行的全面结构、热学和光谱学研究,以便进行比较。虽然所有晶体结构都表现出类似的层状结构和羧酸配位,但在山梨酸钾中,K+ 与 Cα═Cβ 键之间存在额外的非共价相互作用,从而使这种盐具有独特的热特性。反过来,只有酸性山梨酸铵具有[2 + 2]光环加成的预组织,这体现在它在软紫外线照射下的快速非晶化,与其他盐类相反。实验结果结合相关金属羧酸盐以及所研究盐类在食品工业中的应用和分析进行了讨论。
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引用次数: 0
Cluster-Based Bimetallic 3d–4s {CuIn} Metal–Organic Framework for Efficiently Catalyzing Diazotization of Primary Amines 基于簇的双金属 3d-4s {CuIn}用于高效催化伯胺重氮化的金属有机框架
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-24 DOI: 10.1021/acs.cgd.4c0094510.1021/acs.cgd.4c00945
Zhuohao Jiao, Jiale Mu, Ruiquan Guo, Xuechuan Huang, Yan Fu, Fu Hao, Lei Nie*, Lei Wang* and Yuheng Liu*, 

Organic azides are extensively utilized in organic synthesis and clinical drug development. However, the commonly employed catalysts for the preparation of organic azides, such as inorganic salts and simple metal complexes, often suffer from low yields and the production of byproducts. In this study, we report the rational synthesis of a porous, cluster-based bimetallic metal–organic framework (MOF) with a large nanocage of 1 nm in diameter, termed compound 1, designed for this specific reaction. Compound 1 exhibits exceptional solvent stability, remaining stable even in the presence of corrosive triethylamine. Catalytic investigations revealed that compound 1 serves as an effective catalyst for the reaction of primary amines with TfN3, yielding various organic azides under mild conditions. Moreover, this MOF catalyst demonstrates significant catalytic activity for the aminoglycoside drug kanamycin A. The reaction proceeds smoothly with compound 1, producing fewer byproducts and exhibiting good regioselectivity. Additionally, the catalyst can be reused at least five times without a noticeable decrease in catalytic activity. Notably, this represents the first application of MOF materials in the amino diazotization reaction.

有机叠氮化物被广泛用于有机合成和临床药物开发。然而,制备有机叠氮化物常用的催化剂,如无机盐和简单的金属络合物,往往存在产率低和产生副产物的问题。在本研究中,我们报告了一种多孔、基于簇的双金属金属有机框架(MOF)的合理合成,该框架具有直径为 1 nm 的大纳米笼,被称为化合物 1,专为该特定反应而设计。化合物 1 具有优异的溶剂稳定性,即使在具有腐蚀性的三乙胺中也能保持稳定。催化研究表明,化合物 1 是伯胺与 TfN3 反应的有效催化剂,可在温和条件下生成各种有机叠氮化物。此外,这种 MOF 催化剂对氨基糖苷类药物卡那霉素 A 具有显著的催化活性。该反应在化合物 1 的作用下进展顺利,产生的副产物较少,并具有良好的区域选择性。此外,催化剂可重复使用至少五次,而催化活性不会明显降低。值得注意的是,这是 MOF 材料在氨基重氮化反应中的首次应用。
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引用次数: 0
Polymorphism of CL-20 and the Modification and Inhibition Strategies for Its Crystal Transformation CL-20 的多态性及其晶体转化的修饰和抑制策略
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-24 DOI: 10.1021/acs.cgd.4c0106010.1021/acs.cgd.4c01060
Hui Wang, Shifan Xu, Hongtu Zhao, Wenbo Wu, Na Wang*, Ting Wang, Xin Huang, Lina Zhou, Ying Bao* and Hongxun Hao, 

Polymorphism is widespread in energetic materials and has an important influence on the properties of energy materials. 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a typical representative of third-generation energetic materials and the most advanced non-nuclear single explosive currently available, with great potential and application prospects in the charge of new weapons and equipment. In this article, the polymorphic phenomenon and the structure and property of energetic materials are briefly elaborated. Meanwhile, the thermodynamic relationship and phase transition mechanism of the polymorphs are deeply analyzed. Moreover, the research progress of CL-20 polymorphic transformation and its effect on performance is reviewed. The modification and inhibition strategies of CL-20 polymorphic transformation such as coating technology, additive technology, and cocrystal technology are mainly introduced. Furthermore, based on the control method of drug polymorphs, the development trend and the promising perspectives of energetic crystal materials, especially CL-20, are also discussed and proposed.

多态性在能源材料中非常普遍,并对能源材料的性能产生重要影响。2,4,6,8,10,12-六硝基-2,4,6,8,10,12-六氮唑乌齐坦(CL-20)是第三代高能材料的典型代表,也是目前最先进的非核单质炸药,在新型武器装备装药方面具有巨大的潜力和应用前景。本文简要阐述了高能材料的多晶现象、结构与性能。同时,深入分析了多晶体的热力学关系和相变机理。此外,还综述了 CL-20 多晶体转变的研究进展及其对性能的影响。主要介绍了涂层技术、添加剂技术、共晶体技术等 CL-20 多晶体转变的改性和抑制策略。此外,基于药物多晶型的控制方法,还讨论并提出了高能晶体材料,尤其是 CL-20 的发展趋势和前景展望。
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引用次数: 0
Molecular Beam Epitaxy of InAsSbBi Lattice-Matched to InSb toward Long-Wave Infrared Sensing 与 InSb 相匹配的 InAsSbBi 晶格的分子束外延,用于长波红外传感
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-23 DOI: 10.1021/acs.cgd.4c0026410.1021/acs.cgd.4c00264
R. Corey White*, Morgan Bergthold, Aaron Muhowski, Leland Nordin, Iris Okoro, Hussein Hijazi, Leonard Feldman, Daniel Wasserman and Seth R. Bank, 

InSb-based dilute-bismide alloys present a unique opportunity to span the entirety of the long-wave infrared with a bulk, lattice-matched III–V alloy that boasts greatly reduced toxicity compared to the current state-of-the-art, Hg1–xCdxTe. By incorporating both bismuth and arsenic in the appropriate proportions, we demonstrated InAs0.004Sb0.983Bi0.013 lattice-matched to commercially available InSb substrates. A kinetically limited growth regime that combined low substrate temperatures, V/III flux ratios near unity, and a relatively fast growth rate, mitigated phase separation and resulted in films with excellent structural and optical quality. In particular, the bismuth incorporation was estimated to be approximately 95% substitutional and photoluminescence from the alloy was observed at elevated temperatures up to 400 K exhibiting significant wavelength extension beyond that of InSb, out to 7.6 μm at room temperature. Furthermore, the first antimony-rich InAsySb1–xyBix photodetector was fabricated and showed a longer cutoff wavelength than that of an InSb control detector due to the bandgap reduction caused by bismuth and arsenic incorporation. This highlights that emission and detection from InAs0.004Sb0.983Bi0.013 have accessed the longest wavelengths of any lattice-matched, bulk III–V alloy to date. Altogether, these results demonstrate the strong potential of InAsySb1–xyBix for high-performance optoelectronic devices operating across the long-wave infrared.

基于 InSb 的稀双晶合金提供了一个独一无二的机会,利用这种块状、晶格匹配的 III-V 合金,可以跨越整个长波红外线,与目前最先进的 Hg1-xCdxTe 相比,这种合金的毒性大大降低。通过加入适当比例的铋和砷,我们证明了 InAs0.004Sb0.983Bi0.013 与市售 InSb 基底的晶格匹配。结合了低衬底温度、接近统一的 V/III 通量比和相对较快的生长速度的动力学限制生长机制减轻了相分离现象,并产生了具有出色结构和光学质量的薄膜。特别是,据估计铋的取代掺杂率约为 95%,在高达 400 K 的高温下观察到合金发出的光致发光,其波长明显超出了 InSb 的波长,在室温下达到 7.6 μm。此外,还制作出了首个富锑 InAsySb1-x-yBix 光电探测器,由于铋和砷的加入导致带隙减小,该探测器的截止波长比 InSb 对照探测器的截止波长更长。这表明,InAs0.004Sb0.983Bi0.013 的发射和探测波长是迄今为止所有晶格匹配的块状 III-V 合金中最长的。总之,这些结果表明,InAsySb1-x-yBix 具有在长波红外线范围内运行高性能光电器件的巨大潜力。
{"title":"Molecular Beam Epitaxy of InAsSbBi Lattice-Matched to InSb toward Long-Wave Infrared Sensing","authors":"R. Corey White*,&nbsp;Morgan Bergthold,&nbsp;Aaron Muhowski,&nbsp;Leland Nordin,&nbsp;Iris Okoro,&nbsp;Hussein Hijazi,&nbsp;Leonard Feldman,&nbsp;Daniel Wasserman and Seth R. Bank,&nbsp;","doi":"10.1021/acs.cgd.4c0026410.1021/acs.cgd.4c00264","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00264https://doi.org/10.1021/acs.cgd.4c00264","url":null,"abstract":"<p >InSb-based dilute-bismide alloys present a unique opportunity to span the entirety of the long-wave infrared with a bulk, lattice-matched III–V alloy that boasts greatly reduced toxicity compared to the current state-of-the-art, Hg<sub>1–<i>x</i></sub>Cd<sub><i>x</i></sub>Te. By incorporating both bismuth and arsenic in the appropriate proportions, we demonstrated InAs<sub>0.004</sub>Sb<sub>0.983</sub>Bi<sub>0.013</sub> lattice-matched to commercially available InSb substrates. A kinetically limited growth regime that combined low substrate temperatures, V/III flux ratios near unity, and a relatively fast growth rate, mitigated phase separation and resulted in films with excellent structural and optical quality. In particular, the bismuth incorporation was estimated to be approximately 95% substitutional and photoluminescence from the alloy was observed at elevated temperatures up to 400 K exhibiting significant wavelength extension beyond that of InSb, out to 7.6 μm at room temperature. Furthermore, the first antimony-rich InAs<sub><i>y</i></sub>Sb<sub>1–<i>x</i>–</sub><i><sub>y</sub></i>Bi<sub><i>x</i></sub> photodetector was fabricated and showed a longer cutoff wavelength than that of an InSb control detector due to the bandgap reduction caused by bismuth and arsenic incorporation. This highlights that emission and detection from InAs<sub>0.004</sub>Sb<sub>0.983</sub>Bi<sub>0.013</sub> have accessed the longest wavelengths of any lattice-matched, bulk III–V alloy to date. Altogether, these results demonstrate the strong potential of InAs<sub><i>y</i></sub>Sb<sub>1–<i>x</i>–</sub><i><sub>y</sub></i>Bi<sub><i>x</i></sub> for high-performance optoelectronic devices operating across the long-wave infrared.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":null,"pages":null},"PeriodicalIF":3.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142585773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Growth and Piezoelectric Properties of Centimeter-Size BiFeO3 Single Crystals Codoped with Sr and Ti Ions 掺杂锶和钛离子的厘米级 BiFeO3 单晶的生长和压电特性
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-23 DOI: 10.1021/acs.cgd.4c0094410.1021/acs.cgd.4c00944
Qinyu Cao, Jinlun Liang, Liangchen Zhang, Junying Wu, Teng Gao, Xiaolin Hu* and Naifeng Zhuang*, 

A BiFeO3 crystal has both antiferromagnetism and piezoelectricity at room temperature. Unfortunately, it is difficult to grow a larger-size and high-quality BiFeO3 single crystal. By a top-seeded solution growth method using Bi2O3 as a solvent, centimeter-size Bi1–xSrxFe1–yTiyO3 crystals were successfully grown in this paper. Moreover, the lattice symmetry of the Bi1–xSrxFe1–yTiyO3 crystals changes from rhombohedra to cube with the increase in Sr2+ and Ti4+ doping concentration. The magnetization of a Bi0.6Sr0.4Fe0.6Ti0.4O3 crystal reaches 0.25 emu/g at room temperature, which is about 3.1 times as large as that of a BiFeO3 single crystal, in an applied magnetic field of 10,000 Oe. The piezoelectric effect is observed on all Bi0.8Sr0.2Fe0.8Ti0.2O3-2 wafers; especially, strong response was observed on the ⟨111⟩-oriented wafer. By optimizing the type and the concentration of doped ions, it is expected to obtain large-size doped BiFeO3 single crystals with better magnetic and piezoelectric properties.

BiFeO3 晶体在室温下具有反铁磁性和压电性。遗憾的是,较大尺寸和高质量的 BiFeO3 单晶很难生长。本文以 Bi2O3 为溶剂,采用顶籽溶液生长法,成功生长出厘米级尺寸的 Bi1-xSrxFe1-yTiyO3 晶体。此外,随着 Sr2+ 和 Ti4+ 掺杂浓度的增加,Bi1-xSrxFe1-yTiyO3 晶体的晶格对称性从斜方体变为立方体。在室温下,Bi0.6Sr0.4Fe0.6Ti0.4O3 晶体在 10,000 Oe 的外加磁场中的磁化率达到 0.25 emu/g,约为 BiFeO3 单晶的 3.1 倍。在所有 Bi0.8Sr0.2Fe0.8Ti0.2O3-2 晶圆上都观察到了压电效应;尤其是在ɸ111⟩方向的晶圆上观察到了强烈的响应。通过优化掺杂离子的类型和浓度,有望获得具有更好磁性和压电性能的大尺寸掺杂 BiFeO3 单晶。
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引用次数: 0
Growth Mechanism of Hexagonal Zinc Nanocrystals via Liquid Cell Transmission Electron Microscopic 通过液胞透射电子显微镜观察六方锌纳米晶体的生长机理
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-23 DOI: 10.1021/acs.cgd.4c0013210.1021/acs.cgd.4c00132
Rui Zhang, Yubo Wang, Yao Geng, Huxiao Xian, Lipiao Bao* and Xing Lu*, 

Fundamental understanding of the growth mechanism of reactive metal nanomaterials at the atomic level in solutions remains challenging due to the difficulty in observing the growth dynamics of nanoparticles directly through ex situ synthesis methods. Herein, we explore the growth mechanism of hexagonal Zn nanocrystals formed from aqueous precursors using in situ liquid cell transmission electron microscopy for the first time. Real-time observation of growth trajectories of typical Zn nanoparticles reveals the coexistence of classical and nonclassical crystallization mechanisms. Quantitative analysis of the interparticle coalescence suggests that surface diffusion (SD) and grain boundary migration (GBM) are responsible for the shape evolution of coalesced nanoparticles. Analysis of the growth/dissolution kinetics during the Ostwald ripening (OR) process implies that a depletion zone (diffusion layer) around the nanocrystals is present. This study provides fundamental insights into the different stages of the growth mechanism for an important class of reactive metal nanomaterials and is instructive for the controlled synthesis of reactive metal nanomaterials useful in various fields.

由于难以通过原位合成方法直接观察纳米粒子的生长动态,因此要从根本上了解反应性金属纳米材料在溶液中的原子级生长机理仍然具有挑战性。在此,我们首次利用原位液胞透射电子显微镜探索了由水性前驱体形成的六方锌纳米晶体的生长机理。对典型锌纳米粒子生长轨迹的实时观察揭示了经典和非经典结晶机制的共存。颗粒间凝聚的定量分析表明,表面扩散(SD)和晶界迁移(GBM)是凝聚纳米颗粒形状演变的原因。奥斯特瓦尔德熟化(OR)过程中的生长/溶解动力学分析表明,纳米晶体周围存在一个耗竭区(扩散层)。这项研究从根本上揭示了一类重要的活性金属纳米材料不同阶段的生长机理,对可控合成各领域有用的活性金属纳米材料具有指导意义。
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引用次数: 0
Evolution in the Understanding of Noncovalent Interactions Involving Fluorine: From Inception to Maturity to Properties 对涉及氟的非共价相互作用的认识演变:从萌芽到成熟再到特性
IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.1021/acs.cgd.4c0113010.1021/acs.cgd.4c01130
Manish Ranjan Sarkar,  and , Deepak Chopra*, 

Noncovalent interactions play a pivotal role in chemistry, offering versatile tools for manipulating and enhancing various material properties. Among these interactions, the relatively weak, fluorine-centered interactions have emerged as an important contributor in the formation of different crystalline phases and thus hold immense potential in different scientific domains. This comprehensive Perspective delves into the supramolecular chemistry of fluorine-involved interactions, and in particular C–H···F interactions, and explores the evolution in the understanding of the nature of noncovalent interactions, involving fluorine. This is of relevance, as it has implications in the structure and properties of compounds. It has been more than three decades since research began in this area, and it is now well realized that “fluorine does indeed form a hydrogen bond” and also it indeed is “polarizable”. This Perspective elucidates their role in nanotechnology, optical, biological, mechanical, catalytic, and electronic properties as well. Futuristic research could lead to the development of innovative materials and technologies with implications in science and industry. However, it is also important to note that while the potential in different applications exists, much of it is yet to be realized and requires further study.

非共价相互作用在化学中发挥着举足轻重的作用,为操纵和增强各种材料特性提供了多功能工具。在这些相互作用中,相对较弱的以氟为中心的相互作用是形成不同晶相的重要因素,因此在不同科学领域具有巨大的潜力。这本全面的《视角》深入探讨了涉及氟的相互作用,特别是 C-H-F 相互作用的超分子化学,并探讨了对涉及氟的非共价相互作用性质的认识演变。这具有现实意义,因为它对化合物的结构和性质具有影响。自这一领域的研究开始至今已有三十多年,现在人们已经充分认识到 "氟确实能形成氢键",而且它确实 "可极化"。本视角阐明了它们在纳米技术、光学、生物、机械、催化和电子特性方面的作用。未来的研究可能会导致创新材料和技术的开发,并对科学和工业产生影响。不过,同样重要的是要注意到,虽然在不同应用领域存在潜力,但其中大部分尚未实现,需要进一步研究。
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引用次数: 0
期刊
Crystal Growth & Design
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