CrystEngComm最新文献

{"title":"Crystal growth and magnetic properties of hexagonal Ba4CuNb3O12 single crystals†","authors":"Yuhu Huang, Wen Xie, Fei Zheng, Chao Zhang and Han-Shu Xu","doi":"10.1039/D5CE00085H","DOIUrl":"https://doi.org/10.1039/D5CE00085H","url":null,"abstract":"<p >We report a systematic investigation of the growth of high-quality hexagonal perovskite Ba<small>₄</small>CuNb<small>₃</small>O<small>₁₂</small> single crystals using the flux method. The optimal growth involved using the tetragonal phase BaCu<small>_0.33</small>Nb<small>_0.67</small>O<small>₃</small> as the precursor, with 20 g CuO as the flux, a cooling rate of 1 °C h<small>⁻¹</small> between 1350 °C and 1100 °C, and a cooling rate of 2 °C h<small>⁻¹</small> from 1100 °C to 930 °C. The magnetic properties along the <em>ab</em>-plane and the perpendicular direction are thoroughly studied. Fitting the inverse magnetic susceptibility data from 2 K to 300 K with the modified Curie–Weiss (CW) law yields a Weiss temperature (<em>θ</em><small>_CW</small>) of −1.14 K, indicating the presence of antiferromagnetic correlations in the ground state between Cu<small>²⁺</small> ions <em>via</em> superexchange interactions. Furthermore, the specific heat data of Ba<small>₄</small>CuNb<small>₃</small>O<small>₁₂</small> align well with the Debye–Einstein phonon model, allowing us to estimate the Debye temperature of 199 K and the average phonon velocity of 2014.98 m s<small>⁻¹</small>.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 17","pages":" 2711-2719"},"PeriodicalIF":2.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00085h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861055","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Low-temperature synthesis of α-Al2O3via endotaxial transformation from sodium meta-aluminate†","authors":"Fengyong Tian, Jiari He, Jie Wang, Difei Xiao, Zhaoke Zheng, Peng Wang, Yuanyuan Liu, Hefeng Cheng, Ying Dai, Baibiao Huang and Zeyan Wang","doi":"10.1039/D5CE00173K","DOIUrl":"https://doi.org/10.1039/D5CE00173K","url":null,"abstract":"<p >Alpha alumina (α-Al<small>₂</small>O<small>₃</small>), the thermodynamically stable phase of alumina, is widely valued for its exceptional mechanical, thermal, and chemical properties, making it indispensable in applications ranging from abrasives to advanced ceramics. However, conventional synthesis methods require high calcination temperatures (∼1200 °C), leading to energy-intensive processes, particle coarsening, and agglomeration, which limit the production of ultrafine α-Al<small>₂</small>O<small>₃</small> powders. To address these challenges, we propose a novel, low-temperature synthesis route for α-Al<small>₂</small>O<small>₃</small><em>via</em> endotaxial transformation using sodium meta-aluminate (NaAlO<small>₂</small>) as a precursor in the presence of CCl<small>₄</small> under an Ar atmosphere. Leveraging the structural similarity in Al and O atomic arrangements between NaAlO<small>₂</small> and α-Al<small>₂</small>O<small>₃</small>, we demonstrate the successful synthesis of pure α-Al<small>₂</small>O<small>₃</small> at a significantly reduced temperature of 850 °C with a reaction duration of 2 hours and an Ar flow rate of 120 sccm. Systematic investigations reveal that the endotaxial transformation retains the original morphology of the NaAlO<small>₂</small> precursor, offering a potential pathway to control the size and morphology of α-Al<small>₂</small>O<small>₃</small>. This study not only provides a cost-effective and energy-efficient alternative for α-Al<small>₂</small>O<small>₃</small> synthesis but also introduces a scalable strategy for producing high-quality α-Al<small>₂</small>O<small>₃</small> with potential applications in advanced materials and catalysis.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 16","pages":" 2477-2482"},"PeriodicalIF":2.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835486","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A d-glucosamine hydrochloride regulated solvation structure for long life aqueous zinc batteries","authors":"Xiaotong Zhou, Chunru Zhao, Zizhao Liu and Xiang Wu","doi":"10.1039/D5CE00172B","DOIUrl":"https://doi.org/10.1039/D5CE00172B","url":null,"abstract":"<p >In the past decade, aqueous zinc ion batteries (AZIBs) have been developed rapidly in the field of energy storage. However, their practical application is constrained by the issues of severe dendrite growth and side reactions. Herein, we introduce <small>D</small>-glucosamine hydrochloride (DGH) into a ZnSO<small>₄</small> (ZSO) electrolyte to change the solvation structure of Zn<small>²⁺</small>. It effectively impedes the hydrogen evolution reaction (HER) at the electrode/electrolyte interface and restrains dendrite growth at the anode. Moreover, Zn//Zn symmetric cells work stably for 2700 h at 1 mA cm<small>⁻²</small> and 1 mA h cm<small>⁻²</small> with the ZSO + DGH electrolyte. The assembled Zn//NH<small>₄</small>V<small>₄</small>O<small>₁₀</small> batteries deliver an initial capacity of 290.10 mA h g<small>⁻¹</small> at a current density of 5.0 A g<small>⁻¹</small>.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 17","pages":" 2653-2661"},"PeriodicalIF":2.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Acoustic microscopy study on elasto-mechanical properties of Lu3Al5O12:Ce single crystalline films","authors":"Anton Markovskyi, Michał Rosiak, Vitalii Gorbenko, Alexander Fedorov, Mieczysław Ciezko, Zbigniew Szczepański, Yuriy Zorenko, Mariusz Kaczmarek, Jerzy Litniewski and Michał Pakuła","doi":"10.1039/D5CE00068H","DOIUrl":"https://doi.org/10.1039/D5CE00068H","url":null,"abstract":"<p >This article presents experimental, theoretical, and numerical studies of the propagation of guided ultrasonic waves in a layered epitaxial structure of garnet compounds. A microscopic model, which yields dispersion equations based on material and geometrical properties, is developed. Acoustic microscopy experiments on a YAG:Ce crystal substrate and an epitaxial structure containing LuAG:Ce single crystalline films, grown using the liquid phase epitaxy growth method onto a YAG:Ce crystal substrate, reveal distinct phase velocity behaviors. The YAG substrate exhibits consistent velocities, minimally influenced by frequency, while the epitaxial structure shows dispersion, indicating frequency-dependent phase velocities. Experimental results are compared with numerically calculated dispersion curves, showing high agreement in the low-frequency range and minor deviations at higher frequencies. An optimization procedure is developed and applied, starting with the YAG substrate and extending to the LuAG:Ce film/YAG:Ce crystal epitaxial structure. The procedure allows for the extraction of material properties, offering valuable insights into the mechanical characteristics of the all-solid-state LuAG:Ce film/YAG:Ce crystal structure. This research represents a significant advancement in understanding ultrasonic wave dynamics in layered structures, particularly unveiling previously unexplored elastic properties of LuAG:Ce single crystalline films as a well-known scintillation material.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 15","pages":" 2218-2230"},"PeriodicalIF":2.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143786399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aldehyde-based triphenylethylene organic crystals for aniline vapour detection†","authors":"Elissa O. Shehayeb, Abdeljalil Assoud and Vonika Ka-Man Au","doi":"10.1039/D5CE00022J","DOIUrl":"https://doi.org/10.1039/D5CE00022J","url":null,"abstract":"<p >Air pollution, particularly from volatile organic compounds (VOCs), has been a major concern in the past century, especially with the increase in industrial activities. Aniline, one example of VOCs, is mainly involved in the manufacturing industry. Sensing the presence of aniline in prone locations is of great importance due to its hazardous environmental and health implications. This work presents the synthesis of fluorescent organic crystals of a novel compound, an aldehyde derivative of triphenylethylene, namely <strong>TrPE-(CHO)</strong><small>_{<strong>3</strong>}</small>, which can visually portray the presence of aniline vapour by fluorescence quenching. Herein, we investigate the solid-state packing of <strong>TrPE-(CHO)</strong><small>_{<strong>3</strong>}</small> in crystals and its properties, as well as the interactions occurring between the crystals and aniline, and thus elucidate the underlying reason for the selective sensing of aniline as compared to other VOCs. We also demonstrate a proof-of-concept display by coating a light-emitting diode with the synthesized material, which upon exposure to aniline, loses its cyan emission colour.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 16","pages":" 2470-2476"},"PeriodicalIF":2.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00022j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular beam epitaxy of AlGaN nanowires: source configuration and correlated material properties and device characteristics","authors":"Songrui Zhao","doi":"10.1039/D5CE00147A","DOIUrl":"https://doi.org/10.1039/D5CE00147A","url":null,"abstract":"<p >Semiconductor nanowires have emerged as an appealing material platform for cutting-edge semiconductor devices. Behind the exciting progress of semiconductor nanowire devices is the advancement in the understanding of the nanowire synthesis process and mechanism. In this article, I will focus on the recent development in the molecular beam epitaxy (MBE) of semiconductor aluninum gallium nitride (AlGaN) nanowires. MBE has become an attractive tool for large-scale semiconductor nanowire devices, whereas AlGaN is a technologically important semiconductor material for short-wavelength photonics, as well as high-power and radio-frequency (RF) electronics. Different from epilayers wherein only a horizontal surface is involved in the epitaxy, the epitaxial growth of nanowires in general involves both horizontal and vertical surfaces. Such a unique geometry, coupled with different source configurations, greatly affects the growth kinetics, and consequently the material properties and device characteristics. In this regard, the general considerations of MBE chamber configuration for epilayers are discussed first as the basics to understand the nanowire growth. This is followed by the uniqueness of nanowires. In the end, the experimental results regarding to the correlation of source configuration to AlGaN nanowire properties and device characterics such as alloy composition, optical properties, and light emission are discussed. This article could provide useful insight for the development of AlGaN nanowire devices as well as other epitaxial semiconductor nanowire devices beyond AlGaN, especially when the chamber configuration is considered. This article could also shed new light on explaining some features in semiconductor nanowires.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 18","pages":" 2795-2804"},"PeriodicalIF":2.6,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00147a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143908481","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sub-micrometer-thick hydrophobic zeolite corrosion-resistant coatings synthesized using solvothermal secondary growth†","authors":"Ruilan Xu, Yongxuan Wang, Junhui Cai, Rui Wang, Ye Liu, Jingjing Kou, Rongrong Zhang, Xintu Lin and Yong Peng","doi":"10.1039/D5CE00118H","DOIUrl":"https://doi.org/10.1039/D5CE00118H","url":null,"abstract":"<p >Solvothermal secondary growth was used to fabricate zeolite MFI anti-corrosion coatings on a stainless steel plate. Four different diols, <em>i.e.</em>, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, were each investigated as a synthesis solvent. High-quality <em>b</em>-oriented MFI films each with a thickness of 400–500 nm were obtained. The evolution processes and the corresponding characteristics of the zeolite films were compared. FT-IR and XPS analysis of the zeolite surface functional groups demonstrated that the film hydrophobicity mainly originated from the reaction between the diol solvent and the hydrolyzed silica source. The uniform structure and the surface hydrophobicity of the resulting MFI coatings were found to offer good corrosion protection for stainless steel materials.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 15","pages":" 2094-2099"},"PeriodicalIF":2.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143786398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Composition-engineered Yb3+ and Er3+ co-doped bimolybdate and bitungstate mixed crystals for promising solid-state infrared laser application†","authors":"Haitang Hu, Chuancheng Zhang, Yong Zou, Wenpeng Liu and Shoujun Ding","doi":"10.1039/D5CE00083A","DOIUrl":"https://doi.org/10.1039/D5CE00083A","url":null,"abstract":"<p >A series of 10 at% Yb<small>³⁺</small> and 5 at% Er<small>³⁺</small> co-doped NaGd(Mo<small>_<em>x</em></small>W<small>_{1−<em>x</em>}</small>O<small>₄</small>)<small>₂</small> (<em>x</em> = 0.5, 0.7 and 0.9) single crystals was grown <em>via</em> the Czochralski method. X-ray diffraction (XRD), Rietveld refinement and FT-IR analyses were employed to comprehensively analyze the crystal structures. The results firmly established that the crystals belong to the tetragonal system, with the space group identified as <em>I</em>4<small>₁</small>/<em>a</em>. In addition, the 1.5 μm spectral properties of the crystals were investigated, including emission, absorption and fluorescence decay characteristics. Importantly, the study delved deeply into uncovering how the crystal's composition impacts its spectroscopic properties. As the crystal composition changed, there was a notable inhomogeneous broadening of the spectral line. A maximum full width at half-maximum (FWHM) of 83 nm at 1535 nm was obtained for the Yb,Er:NaGd(Mo<small>_0.5</small>W<small>_0.5</small>O<small>₄</small>)<small>₂</small> crystal. However, the maximum absorption and emission cross-sections were achieved in the Yb,Er:NaGd(Mo<small>_0.7</small>W<small>_0.3</small>O<small>₄</small>)<small>₂</small> crystal, with values of 1.15 × 10<small>⁻²⁰</small> cm<small>²</small> and 1.05 × 10<small>⁻²⁰</small> cm<small>²</small>, respectively. Besides, for the Yb,Er:NaGd(Mo<small>_0.7</small>W<small>_0.3</small>O<small>₄</small>)<small>₂</small> crystal, a positive gain cross-section was obtained at around 1535 nm for a population inversion ratio (<em>β</em>) of &gt;0.4. These results show that double molybdate/tungstate mixed crystals co-doped with Yb<small>³⁺</small> and Er<small>³⁺</small> are promising for 1.5 μm near-infrared solid-state laser application.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 17","pages":" 2662-2671"},"PeriodicalIF":2.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143861041","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mononuclear high-spin Fe(iii) complexes: synthesis, crystal structures, magnetic and optical properties†","authors":"Olga Danilescu, Paulina Bourosh, Ion Bulhac, Olga Kulikova, Maria Cocu and Yurii Chumakov","doi":"10.1039/D5CE00125K","DOIUrl":"https://doi.org/10.1039/D5CE00125K","url":null,"abstract":"<p >The coordination agent H<small>₂</small>L = 2,6-diacetylpyridine bis(picolinoylhydrazone) was used for the synthesis of two mononuclear iron(<small>III</small>) complexes [Fe(H<small>₂</small>L)(H<small>₂</small>O)<small>₂</small>]X<small>₃</small>·2.5H<small>₂</small>O, where X = NO<small>₃</small><small>⁻</small> (<strong>1</strong>) and ClO<small>₄</small><small>⁻</small> (<strong>2</strong>). In the studied crystals of <strong>1</strong> and <strong>2</strong>, characterized by IR spectroscopy and X-ray diffraction, the pentadentate Schiff base ligands are coordinated in mononuclear cationic complexes [Fe(H<small>₂</small>L)(H<small>₂</small>O)<small>₂</small>]<small>³⁺</small> by donor atoms N<small>₃</small>O<small>₂</small> as double zwitterions. In <strong>1</strong>, the cations are joined to centrosymmetric dimers <em>via</em> hydrogen bonds (HB), forming chains in the crystal, while in <strong>2</strong>, the cations are assembled into tetramers through HB owing to the anions and water molecules. The crystal structures of the studied compounds were stabilized <em>via</em> hydrogen bonding that yielded supramolecular 3D networks <em>via</em> coordinated and crystallization water molecules, PyH<small>⁺</small> groups of H<small>₂</small>L and NO<small>₃</small><small>⁻</small> or ClO<small>₄</small><small>⁻</small> anions. The theoretical calculations, performed using the new DFT-TB2J approach revealed the magnetic exchange interactions between the iron ions, which were mediated through intermolecular hydrogen bonds. The UV-vis absorption spectra of <strong>1</strong> and <strong>2</strong> were not overlapped with their photoluminescence emission spectra because of the spin-gapless characteristic of the band structure of these compounds.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 19","pages":" 3006-3017"},"PeriodicalIF":2.6,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143944068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Inorganic salts of topiroxostat: metastable tautomeric form and improved pharmaceutical performance†","authors":"Jiangying Li, Haowen Ma, Xiaoju Shi, Ting Jiao, Lin Wang, Meiling Nie, Xiaojuan Wang, Zongwu Deng and Hailu Zhang","doi":"10.1039/D5CE00073D","DOIUrl":"https://doi.org/10.1039/D5CE00073D","url":null,"abstract":"<p >Tautomerism is a phenomenon where a compound may exist in two or more interconvertible structural isomers (known as tautomers) that are generally different in terms of the relative position of one hydrogen atom. Tautomeric pharmaceuticals have more potential solid forms, thereby expanding the range of options for modulating their physicochemical properties in the solid state. All crystal structures of topiroxostat (TOP) polymorphs solved previously and in this contribution reveal that the TOP molecule monotonically exists in the 2<em>H</em>-tautomeric form. After salt formation with hydrochloric acid (TOP–HCl–H<small>₂</small>O) or sulfuric acid (TOP–H<small>₂</small>SO<small>₄</small> form I and form II), the protonated 3<em>H</em>-tautomeric form was observed. Compared with TOP, all three salt forms demonstrated improved dissolution performance and TOP–HCl–H<small>₂</small>O also displayed satisfactory moisture stability. It is noteworthy that hydrochloric acid and sulfuric acid are the most commonly used salt formers for commercial pharmaceuticals. The proven safety of the counterions and improved pharmaceutical performance of TOP salts highlight their potential for further pharmaceutical applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 16","pages":" 2534-2544"},"PeriodicalIF":2.6,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}