CrystEngComm最新文献

{"title":"Controllable preparation of cation vacancy-modulated oxygen defect Mn2−xP2O7−y anodes to enhance lithium storage performance†","authors":"Zhengen Sun, Ning Zhang, Yanjun Cai, Qingrong Kong, Xiang Yao, Hualing Tian, Ziyun Ma, Yang Zhang and Zhi Su","doi":"10.1039/D4CE01263A","DOIUrl":"https://doi.org/10.1039/D4CE01263A","url":null,"abstract":"<p >Oxygen-deficient Mn<small>_{2−<em>x</em>}</small>P<small>₂</small>O<small>_{7−<em>y</em>}</small> with modulated cation vacancies was synthesized using a solvothermal method; through the synergistic influence of these vacancies, the optimized manganese pyrophosphate anode (Mn<small>_1.93</small>P<small>₂</small>O<small>_{7−<em>y</em>}</small>) exhibited enhanced electrochemical properties.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 10","pages":" 1377-1380"},"PeriodicalIF":2.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535718","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":"Solubility of polymorphic glycine in mixed solutions with molecular dynamics simulation and thermodynamic analysis†","authors":"Zhihao Wang, Yixin Ma, Yan Zhang, Li Yang, Songlin Zheng, Jingcai Cheng and Chao Yang","doi":"10.1039/D5CE00018A","DOIUrl":"https://doi.org/10.1039/D5CE00018A","url":null,"abstract":"<p >A deep insight into the solubility behavior of glycine is essential for optimizing its application in the fields such as pharmaceutical formulations and crystallization. Although the solubility of glycine has been extensively studied, the solubility of polymorphic glycine in mixed solvents still needs to be further investigated, especially in the presence of impurities. In this study, the solubility of polymorphic glycine in three mixed solutions (water–methanol, water–methanol–NH<small>₄</small>Cl, and water–methanol–HMTA) was determined using <em>in situ</em> ATR-FTIR over the temperature range of 293.15 to 333.15 K. The solubility of glycine decreased with increasing methanol concentration. And it is enhanced with the increase of NH<small>₄</small>Cl concentration, while the addition of hexamethylenetetramine inhibited the dissolution of glycine. The modified Apelblat equation, the <em>λh</em> equation and the non-random two-liquid (NRTL) model were utilized to correlate the experimental solubility data. All the models produce good correlations for the solubility data. Molecular dynamics simulation was employed to calculate intermolecular interactions to better understand the glycine dissolution behavior. The solvation free energy indicated that the solubility of glycine increased with the increase of solute–solvent interaction. The presence of impurities significantly affects the solvation free energy of glycine, thus impacting the glycine solubility. Radial distribution function analysis further demonstrated that impurities also impacted the interaction between water molecules and altered the interactions between glycine and water molecules. In addition, the apparent standard thermodynamic properties (Δ<small>_sol</small><em>H</em><small>⁰</small>, Δ<small>_sol</small><em>S</em><small>⁰</small>, and Δ<small>_sol</small><em>G</em><small>⁰</small>) of glycine in the three mixed solutions were calculated using the van't Hoff equation. The results revealed that glycine dissolution is both endothermic and entropy-driven, with enthalpy being the primary contributor to the Gibbs free energy variation during dissolution.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 10","pages":" 1446-1459"},"PeriodicalIF":2.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535732","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":"Expression of concern: The behavior of Ni nanotubes under the influence of environments with different acidities","authors":"Maksim D. Kutuzau, Egor Yu. Kaniukov, Elena E. Shumskaya, Victoria D. Bundyukova, Gulnar R. Kalkabay, Maxim V. Zdorovets, Daryn B. Borgekov and Artem L. Kozlovskiy","doi":"10.1039/D5CE90023A","DOIUrl":"https://doi.org/10.1039/D5CE90023A","url":null,"abstract":"<p >Expression of Concern for ‘The behavior of Ni nanotubes under the influence of environments with different acidities’ by Maksim D. Kutuzau <em>et al.</em>, <em>CrystEngComm</em>, 2018, <strong>20</strong>, 3258–3266, https://doi.org/10.1039/C8CE00362A.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 8","pages":" 1214-1214"},"PeriodicalIF":2.6,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce90023a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430605","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":"Tailoring nanostructured NiFe-LDH catalysts via ammonium fluoride-mediated hydrothermal synthesis: enhanced electrocatalytic performance in oxygen evolution reactions†","authors":"Xinyi Feng, Xiaodong Hao, Xuan Zhao, Yangchun Guo, Shufang Ma, Bingshe Xu, Hui Liu and Bo Gao","doi":"10.1039/D4CE01298D","DOIUrl":"https://doi.org/10.1039/D4CE01298D","url":null,"abstract":"<p >The performance of NiFe-layered double hydroxides (LDHs) as electrocatalysts for the oxygen evolution reaction (OER) can be significantly enhanced through precise structural and compositional modifications. In this study, ammonium fluoride (NH<small>₄</small>F) was introduced as an effective reagent to tune the microstructure and cation distribution of NiFe-LDHs, which in turn influenced their OER activity. Through a one-step hydrothermal synthesis method, NiFe-LDHs were fabricated with varying amounts of NH<small>₄</small>F. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis revealed a shift in the oxidation states of Ni and Fe, with an increase in the proportion of high-valent cations in the NFL-7F sample. This shift was closely correlated with enhanced OER performance. Detailed characterization through scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical tests demonstrated that the NFL-7F sample exhibited the best OER performance, including superior stability and activity, compared to other samples. The results indicate that NH<small>₄</small>F plays a crucial role in optimizing the electronic structure and morphology of NiFe-LDHs, thereby facilitating enhanced OER kinetics. This study provides valuable insights into the structure–performance relationship of NiFe-LDH catalysts and highlights the importance of tuning the oxidation states of metal cations for the development of efficient electrocatalysts.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 10","pages":" 1483-1490"},"PeriodicalIF":2.6,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535735","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":"Phosphorus-incorporated layered carbon nitride films and their electronic and magnetic properties†","authors":"Natsuko Kurimoto, Noriyuki Urakami, Yoshio Hashimoto and Xiaoxi Liu","doi":"10.1039/D4CE01103A","DOIUrl":"https://doi.org/10.1039/D4CE01103A","url":null,"abstract":"<p >Layered carbon nitride (g-C<small>₃</small>N<small>₄</small>) is a semiconducting material that is used in electronic applications, and its physical and chemical properties can be improved by incorporating foreign atoms. We prepared highly ordered P-incorporated g-C<small>₃</small>N<small>₄</small> crystalline films <em>via</em> chemical vapor deposition using powder sources and then studied their electronic and magnetic properties. The optical absorption edge shifted to the low-energy side with incorporation of increasing P content, which indicated a narrow energy bandgap. Analysis of the chemical bonding <em>via</em> X-ray photoelectron spectroscopy revealed that P atoms were incorporated into the nearest-neighbor C sites of the N atoms bridging the heptazine units. No significant degradation of crystallinity was observed when the substrate temperature was below 620 °C and P composition was below 10%. Furthermore, n-type conductivity was achieved because the P atoms incorporated into the C sites acted as donor impurities. A giant anisotropy of electron transport with a dependence on the crystal orientation was demonstrated, leading to low out-of-plane and high in-plane resistivities with anisotropy ratios above 4 × 10<small>⁵</small>. The activation energy for electron generation was estimated to be approximately 102.5 meV from the temperature dependence of resistivity. Notably, ferromagnetism without metallic elements was observed at room temperature. In addition, anisotropic ferromagnetism was observed along the out-of-plane and in-plane directions, which were large and small saturation magnetizations, respectively.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1599-1606"},"PeriodicalIF":2.6,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602079","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":"The influence of the crystal sponge framework on guest molecule conformation†","authors":"Eleanor M. Soper, Simon J. Coles and Graeme M. Day","doi":"10.1039/D4CE00699B","DOIUrl":"https://doi.org/10.1039/D4CE00699B","url":null,"abstract":"<p >The crystalline sponge (CS) method has become an important technique for structural elucidation of compounds that are challenging to crystallise. The impact of the CS environment on guest molecule conformations has not been systematically studied. We present a computational investigation of the conformations of organic molecules of varying flexibility in a set of experimentally determined CS structures, comparing them to gas phase conformers and, where available, pure and co-crystal structures. <em>Via</em> solid state and molecular density functional theory calculations, we quantify the total relative energy, conformational energy, and intramolecular strain of guest molecules, as well as framework strain. Our results show that while CS structures induce distortion in guest geometries (total relative energies up to 41 kJ mol<small>⁻¹</small>), they generally adopt low-energy conformations, often within 2 kJ mol<small>⁻¹</small> of the global energy minimum. Intramolecular strain in CS structures is often lower than in conventional crystal structures, suggesting a more neutral packing environment where molecules are closer to their favoured isolated-molecule geometries. We also observe that multiple guests can influence each other's geometries, even in the absence of direct guest–guest interactions. These findings provide a quantification of conformational distortion that can form the basis for interpreting molecular geometries obtained from CS structures.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 10","pages":" 1491-1502"},"PeriodicalIF":2.6,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce00699b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143535736","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":"Photochromic pyridylfulgenates and their cadmium complexes†","authors":"Ying-Ying Mai, Li Liu and Jing-Cao Dai","doi":"10.1039/D4CE01219D","DOIUrl":"https://doi.org/10.1039/D4CE01219D","url":null,"abstract":"<p >In this work, two novel photochromic pyridylfulgenate molecules, Fulg1 and Fulg2, were successfully synthesized as photosensitive ligands. Their further reactions with Cd<small>²⁺</small> species resulted in four interesting cadmium–fulgenate frameworks, namely, [Cd<small>₂</small>(Fulg1)<small>₄</small>(DMF)]<small>_<em>n</em></small> (<strong>1</strong>), [Cd(Fulg1′)(HCO<small>₂</small>)]<small>_<em>n</em></small> (<strong>2</strong>), [Cd(Fulg1′)<small>₂</small>(H<small>₂</small>O)<small>₂</small>]<small>_<em>n</em></small> (<strong>3</strong>), and {[Cd(Fulg2)<small>₂</small>(H<small>₂</small>O)]·H<small>₂</small>O}<small>_<em>n</em></small> (<strong>4</strong>). It was observed that the molecular packing of both Fulg1 and Fulg2 was a 1D infinite zigzag supramolecular chain linked <em>via</em> hydrogen bonding interactions. X-ray crystallographic studies revealed the crystal packing of the four cadmium–fulgenate frameworks as follows: a 2D 4,4-linked topological network for both <strong>1</strong> and <strong>4</strong>, a 1D fishtrap-like cage chain with an inner cavity diameter of 6.3 Å for <strong>2</strong>, and a 1D metallalooper-like chain for <strong>3</strong>. Upon irradiation using a UV lamp, either Fulg1 or Fulg2 exhibited an excellent photochromic property with a rapid crystalline color conversion from colorless to blue for Fulg1 and to pale purple for Fulg2, which were confirmed by spectroscopic investigation and theoretical calculations. In contrast, their cadmium complexes (compounds <strong>1–4</strong>), exhibited extremely low photosensitivity. The experimental observations demonstrated that the inflexible conformation of chromophore units caused by the coordinated cadmium centers and the resulting diverse structural features of these pyridylfulgenate compounds are mainly responsible for their significant differences in the photosensitivity.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1548-1559"},"PeriodicalIF":2.6,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602091","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":"Hierarchical Zn3(OH)2V2O7·2H2O microsphere adsorbents for highly-efficient removal of Pb2+","authors":"Miao Wang, Kelin Liu, Qing Huang, Huimin Zu, Congrong Lv, Yanfeng Tang and Tongming Sun","doi":"10.1039/D4CE01142B","DOIUrl":"https://doi.org/10.1039/D4CE01142B","url":null,"abstract":"<p >Developing new, high-efficiency and low-cost adsorbents is of significant importance for efficient removal of contaminants from wastewater. Herein, hierarchical nanowire-assembled Zn<small>₃</small>(OH)<small>₂</small>V<small>₂</small>O<small>₇</small>·2H<small>₂</small>O microspheres (ZVO Ms) are prepared by a facile <small>L</small>-threonine (<small>L</small>-Thr) assisted hydrothermal method and explored as nano-adsorbents for the removal of Pb<small>²⁺</small> from simulated wastewater. A formation mechanism is proposed based on the morphological evolution. The optimal ZVO Ms demonstrate satisfactory adsorption performance for Pb<small>²⁺</small> with a maximum adsorption capacity of 461.6 mg g<small>⁻¹</small>, and the removal efficiency is approximately three times higher than that of nanosheet-assembled ZVO Ms obtained in the absence of <small>L</small>-Thr. The adsorption isotherms and kinetics were well described by the Langmuir isotherm model and the pseudo-second-order model, respectively. The thermodynamic data indicate that Pb<small>²⁺</small> adsorption is an endothermic and spontaneous chemical adsorption process. The adsorption mechanism is uncovered based on electrostatic attraction and ion exchange. The excellent adsorption performance may be attributed to unique hierarchical structures and higher surface areas, which accelerate the transport of reactant molecules and provide abundant active sites for adsorption of Pb<small>²⁺</small>. This work provides a reasonable strategy to prepare novel hierarchical micro/nanoarchitectures and the as-prepared ZVO adsorbent may be used as a candidate for the removal of Pb<small>²⁺</small> contaminants in wastewater.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 9","pages":" 1276-1281"},"PeriodicalIF":2.6,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143475049","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":"Correction: The Sc2WxMo3−xO12 series as electrodes in alkali-ion batteries","authors":"Junnan Liu, Bernt Johannessen, Helen E. A. Brand, Henrik L. Andersen and Neeraj Sharma","doi":"10.1039/D5CE90018B","DOIUrl":"https://doi.org/10.1039/D5CE90018B","url":null,"abstract":"<p >Correction for ‘The Sc<small>₂</small>W<small>_<em>x</em></small>Mo<small>_{3−<em>x</em>}</small>O<small>₁₂</small> series as electrodes in alkali-ion batteries' by Junnan Liu <em>et al.</em>, <em>CrystEngComm</em>, 2021, <strong>23</strong>, 3880–3891, https://doi.org/10.1039/D1CE00318F.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 7","pages":" 1044-1044"},"PeriodicalIF":2.6,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce90018b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379659","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":"The optimization of hydrogen evolution performance by removing guest molecules in Co-MOF†","authors":"Xiang-Yu Chen, Zi-Ang Hu, Yan Qu, Ru-Jin Ning, Wen-Da Tao, Shou-Qin He, Zhi-Fu Liu, Yong-Hui Shen and Ling Qin","doi":"10.1039/D5CE00014A","DOIUrl":"https://doi.org/10.1039/D5CE00014A","url":null,"abstract":"<p >In order to solve the current energy crisis, the improvement of hydrogen evolution electrocatalysts is a very effective way. Herein, one cobalt-based metal–organic framework (Co-PIPA, PIPA = 5-(pyridin-4-yl)isophthalic acid) with 4,4′-dibromo-1,1′-biphenyl as guest molecules was synthesized. Next, we removed the guest molecules in the channels by soaking the Co-PIPA in ethanol (named Co-PIPA-ethanol). Co-PIPA and Co-PIPA-ethanol were pyrolyzed to obtain the derived material, Co-PIPA-T and Co-PIPA-ethanol-T. Their electrocatalytic hydrogen evolution results confirmed that Co-PIPA-ethanol-T has a better hydrogen evolution performance. This work provides the possibility for further regulating the pore channels of the catalyst to optimize the electrocatalytic performance.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1591-1598"},"PeriodicalIF":2.6,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602078","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}