Dalton Transactions最新文献

{"title":"Study of Methylene Blue removal and photocatalytic degradation on Zirconia Thin Films Modified with Mn-Anderson-Polyoxometalates","authors":"Jiress Florez, Carlos Enrique Diaz-Uribe, William Vallejo, Freider Duran, Esneyder Puello, Javier Salazar, Ximena Zárate, Eduardo Schott","doi":"10.1039/d4dt02782e","DOIUrl":"https://doi.org/10.1039/d4dt02782e","url":null,"abstract":"Recalcitrant pollutants are hard to degrade compounds during water treatments. Methylene Blue (MB) is a cationic dye that is environmentally persistent. Heterogeneous photocatalysis has become in a suitable strategy to remove this kind of pollutant from water. In this work, ZrO2 thin films were modified with Anderson-type Mn-Polyoxometalate (MnPOM) (with formula (NH4)3[MnMo6O24H6]) and the MB remotion efficiency from water was studied. ZrO2 was synthesized by sol gel method, the thin films were deposited by Doctor Blade method and, ZrO2 thin films were modified using chemisorption method. The obtained materials were characterized by SEM, EDX, UV-Vis diffuse reflectance and FTIR. The adsorption kinetics and isotherms of MB were studied for both materials (bare ZrO2 and ZrO2/MnPOM). The optical characterization showed a band gap energy of 4.02 eV for bare ZrO2 while the energy band gap value for ZrO2/MnPOM was 3.7 eV. Also, the ZrO2 showed less MB removal capacity (~8 %) than ZrO2/MnPOM thin films (~29 %). The isothermal assay indicated that MB adsorption onto bare ZrO2 and ZrO2/MnPOM is better described by the Langmuir model (qm= 20.6 mg/g for ZrO2 and qm= 62.9 mg/g for ZrO2/MnPOM). Furthermore, a pseudo second order model was suitable to describe the kinetic of the MB adsorption process. The photocatalytic tests show an apparent constant rate (kap) value of 2 x10-3 min-1 for bare ZrO2 and a value of kap 5.4 x10-3 min-1 for ZrO2/MnPOM after 100 minutes using UV irradiation. TD-DFT calculations revealed a LMCT between the ZrO2 nanoparticle and the MnPOM, explaining the enhanced photocatalytic activity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"20 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793614","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: Metallomesogens based on platinum(ii) complexes: synthesis, luminescence and polarized emission","authors":"Yafei Wang, Yu Liu, Jian Luo, Hongrui Qi, Xiaoshuang Li, Meijun Nin, Ming Liu, Danyan Shi, Weiguo Zhu and Yong Cao","doi":"10.1039/D4DT90181A","DOIUrl":"10.1039/D4DT90181A","url":null,"abstract":"<p >Correction for ‘Metallomesogens based on platinum(<small>II</small>) complexes: synthesis, luminescence and polarized emission’ by Yafei Wang <em>et al.</em>, <em>Dalton Trans.</em>, 2011, <strong>40</strong>, 5046–5051, https://doi.org/10.1039/C0DT01515F.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 1","pages":" 416-416"},"PeriodicalIF":3.5,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d4dt90181a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793616","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":"Phosphorus-containing polycarbosilazanes: Synthesis via dehydrocoupling catalysis and flame-retardant properties","authors":"Albert Soran, Peter Chapple, Claire Longuet, Rodolphe Sonnier, Marie Cordier, Jean Francois Carpentier, Yann Sarazin","doi":"10.1039/d4dt03172e","DOIUrl":"https://doi.org/10.1039/d4dt03172e","url":null,"abstract":"The barium complex [Ba{N(SiMe<small>₃</small>)<small>₂</small>}<small>₂</small>]<small>₂</small> has been used to catalyse the dehydropolymerisation of the phosphine-functionalised hydrosilane 4-Ph<small>₂</small>P-C<small>₆</small>H<small>₄</small>SiH<small>₃</small> (<strong>A</strong>) with the α,ω-diamine 1,4-(CH<small>₂</small>NHMe)<small>₂</small>-C<small>₆</small>H<small>₄</small> (<strong>C</strong>), for the production of -[Si(4-C<small>₆</small>H<small>₄</small>PPh<small>₂</small>)H-N(Me)CH<small>₂</small>-C<small>₆</small>H<small>₄</small>-CH<small>₂</small>N(Me)]<small>_n</small>- polycarbosilazanes that contain dangling phosphino groups along the polymer backbone. The comonomers <strong>A</strong> and <strong>C</strong>, specifically prepared for this purpose and comprehensively characterised, lend themselves well to barium-promoted dehydrocoupling catalysis. They allow for the formation of linear, amine-capped polymers with molecular weights in the range 4,000-8,000 g mol<small>^–1</small>, as estimated by DOSY and <small>¹</small>H endgroup NMR analyses. The terpolymerisation of <strong>C</strong> with various mixtures of <strong>A</strong> and PhSiH<small>₂</small>R (R = H or Ph) led to the formation of terpolymers featuring various contents of phosphine-functionalised silazane groups, with an overall composition that reflects well the initial feed ratio of the comonomers. Thermal decomposition and flammability were studied at microscale on a series of polycarbosilazanes to assess the effect of molecular groups on thermal stability and heat release. The SiCN backbone containing silazane group significantly contributes to the “charring” of the polymer. By contrast, PPh<small>₂</small>, as other groups bearing a phosphorus atom in a low oxidation state, is not an effective char promoter.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"69 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793417","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":"Constructing dendrite-suppressing separator based on cellulose acetate and polyoxometalates toward uniform lithium electrodeposition","authors":"Xi-Yue Zhang, Jia-Yuan Zhang, Gui Wang, Chun-Hui Zhang, Lin-Lin Fan, Yun-Dong Cao, Hong Liu, Guanggang Gao","doi":"10.1039/d4dt03157a","DOIUrl":"https://doi.org/10.1039/d4dt03157a","url":null,"abstract":"The functionalized separator is expected to serve as a protective barrier to conquer the lithium dendrite penetration in lithium metal batteries. Herein, a novel self-supporting separator material has been successfully synthesized based on the cellulose acetate and Keggin-type polyoxometalate H3PMo12O40xH2O (marked as CA/PMo12). The incorporation of PMo12 facilitates the transformation of the original finger-like structure of CA separator into a uniform three-dimensional porous grid architecture, which is more effective in inhibiting the growth of lithium dendrites. For the obtained CA/PMo12 separator, the mechanical strength, electrolyte uptake capacity, and Li+ anchoring ability have been significantly improved. The plentiful ether and carbonyl functional groups of CA can effectively adsorb lithium ions and regulate the uniform lithium plating. More significantly, density functional theory calculation shows that the coordination environment formed between PMo12 and CA is conducive to enhancing the adsorption ability of lithium ions and promoting the rapid migration of lithium ions. Meanwhile, PMo12 can act as an “ion sponge” to form a lithium-rich layer, making the distribution of charges on the lithium surface more uniform, while undergoing the reversible transformation between its reduced and oxidized states during repeated plating/stripping processes. Consequently, the Li//Li symmetrical cell using CA/PMo12 separator shows excellent plating/stripping efficiency after 1075 cycles with a low hysteresis voltage of 38.1 mV under 5 mA cm-2 and 1 mAh cm-2. Meanwhile, LiFePO4//Li cell achieves the superior reversible capacity of 90 mAh g-1 after 100 cycles under 1 C.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"210 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793617","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":"Extraction and Complexation of Trivalent Americium and Lanthanides by an Asymmetric Picolinic Acid-derived Tridentate N,O-hybrid ligand","authors":"Hong Cao, Yuxiao Guo, Bin Li, Qilong Tang, Huai Xin Hao, Zhipeng Wang, Chao Xu","doi":"10.1039/d4dt03016h","DOIUrl":"https://doi.org/10.1039/d4dt03016h","url":null,"abstract":"The extraction and complexation of trivalent americium (Am) and lanthanides (Ln) by an asymmetric picolinic acid-derived tridentate N,O-hybrid ligand, 6-(dioctylcarbamoyl)picolinic acid (DOAPA), have been studied through both experimental and theoretical methods. DOAPA exhibits effective and fast extraction of Am(III) and Ln(III). The extraction is driven by favorable enthalpy change. Slope analysis, absorption spectroscopy and NMR titration indicate that both Am(III) and Ln(III) coordinate with DOAPA to form complexes of a 1:3 stoichiometry (metal to ligand). Meanwhile, luminescence and mass spectra studies suggest that three deprotonated tridentate DOAPA ligands (L-) substitute all the H2O molecules in the primary coordination sphere of Eu(III), resulting in the extraction of a neutral complex into the organic phase. Further theoretical calculations reveal that more robust interaction between DOAPA and Am(III) relative to Eu(III) as well as higher degree of covalence in Am-N/O bonds than that in Eu-N/O bonds leads to slight selectivity of Am(III) over Eu(III).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"140 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793619","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":"Fluorescent Zinc(II) Thione and Selone Complexes for Light-Emitting Applications","authors":"Suman Mandal, Bikash Lahkar, Gopendra Muduli, Arushi Rawat, Abhilash Sahu, Osamu Tsutsumi, Ganesan Prabusankar","doi":"10.1039/d4dt02924k","DOIUrl":"https://doi.org/10.1039/d4dt02924k","url":null,"abstract":"Three 1-(anthracene-9-ylmethyl)-3-isopropyl-imidazol-2-thione Zn(II) halide complexes (1-3), and one 1-(anthracene-9-ylmethyl)-3-isopropyl-imidazol-2-selone Zn(II) dichloride complex (4) have been synthesized and characterized. Complexes 2, 3, and 4 have distorted tetrahedral geometry, while complex 1 has tetrahedral geometry. All these complexes displayed emission in the crystalline state, with complex 3 showing emission in the yellow region and 1 and 4 in the blue, while 2 gave bluish-green emission. The ligands L1 and L2 were non-emissive in both solution and crystalline state. The photophysical behavior of these four complexes was studied and the quantum yield in crystalline state was obtained. Complex 1 gave the highest quantum yield of 7.72% and 2 and 3 gave 5.95%, and 5.07% respectively. Complex 4 has a relatively lesser quantum yield (3.87%). The crystalline state quantum yield for the complexes varies with the variation of the halide coordinated to the metal center as Clˉ &gt; Brˉ &gt; Iˉ. The quantum yield for the thione complexes 1-3 is found to be better than the selone complex 4. Density functional theory calculations have been performed to study their structural properties and emissive natures. TD-DFT natural transition orbital calculations reveal that intra-ligand charge transfer (1ILCT) mediated through the metal center is responsible for the observed emission behavior.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"61 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793688","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":"Na2B12Si6Se18: A Novel B12-Cluster-containing Quaternary Selenoborate Framework Material","authors":"Gopabandhu Panigrahi, Hunter B Tisdale, Gregory Morrison, Hans-Conrad Zur Loye","doi":"10.1039/d4dt03139c","DOIUrl":"https://doi.org/10.1039/d4dt03139c","url":null,"abstract":"We report the successful synthesis of the new quaternary, three-dimensional Na₂Si₆B₁₂Se₁₈ material using a solid-state synthesis route. This compound is characterized by a unique framework structure that features the rare icosahedral [B12]10+ cation which is connected via Si2Se6 polyhedral units into a 3D framework structure with Na⁺ ions located inside the channels. The Na2Si6B12Se18 compound crystallizes in the cubic crystal system in the space group Im¯3, with lattice parameter a = 11.91110(10) Å and unit cell volume of 1689.88(4) ų. The 3D framework of the [Si6B12Se18]²⁻ anion contains B₁₂ icosahedra with six of their edges bridged by tetrahedral SiSe4 groups. The B12 icosahedral units are connected by the SiSe4 tetrahedral units which bridge between each B₁₂ icosahedron. Ultraviolet-Visible (UV-vis) spectroscopy revealed that Na2Si6B12Se18 exhibits semiconducting behavior with an estimated bandgap of 2.1(1) eV. In-situ powder X-ray diffraction (PXRD) studies were conducted to investigate the phase formation of this compound as a function of temperature to obtain information of its thermal stability and structural evolution.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"60 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793615","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":"Modification of CoMoO4 by Fe doping strategy for efficient electrolysis of water","authors":"Guangzheng Xu, Yin Huang, Jing Peng, Lina Yu, Xiuhua Wang","doi":"10.1039/d4dt03252g","DOIUrl":"https://doi.org/10.1039/d4dt03252g","url":null,"abstract":"Hydrogen is one of the ideal alternative energy sources as a non-polluting and clean energy source. The main commercial materials used for hydrogen production from electrolytic water are precious metals. Its high price has a negative impact on the industrialisation of electrolytic water, and there is an urgent need to research highly active and durable non-precious metal materials to replace it. The inorganic transition metals are of interest due to their high content and low price. Here, we have prepared high performance and stable Fe-CoMoO4 by modifying the geometrical and electronic structures of cobalt molybdate. The overpotential of hydrogen precipitation is only 42 mV at a current density of 10 mA cm-2 in 1 M KOH solution. Meanwhile, it can be stabilised for 32 h at a current density of 100 mA cm-2. This work provides a new approach to the study of non-precious metal-based catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"83 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793624","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":"High-Pressure Phase Transition and Amorphization of BaV2O6","authors":"Peijie Zhang, Pablo Botella Vives, Neha Bura, Jose-Luis Rodrigo, Josu Sanchez-Martin, David Vie, Catalin Popescu, Daniel Errandonea","doi":"10.1039/d4dt03091e","DOIUrl":"https://doi.org/10.1039/d4dt03091e","url":null,"abstract":"The structural evolution of metavanadate compounds under high pressure offers valuable insights into phase transitions and changes in material properties. This study explores the structural behavior of BaV<small>₂</small>O<small>₆</small> under pressures up to 12 GPa using powder X-ray diffraction and density-functional theory (DFT) simulations. The results indicate a phase transition from the ambient pressure orthorhombic phase (space group <em>C</em>222) to a monoclinic phase (space group <em>C</em>2) at 4 GPa, likely driven by distortion of the vanadium oxide polyhedron. Above 10 GPa, the <em>C</em>2 phase undergoes amorphization, attributed to the breakdown of the infinite [VO<small>₄</small>] chains into [VO<small>₃</small>]<small>^-</small> units. Additionally, BaV<small>₂</small>O<small>₆</small> exhibits anisotropic lattice contraction and a relatively low bulk modulus (<em>B₀</em> ≈ 50 GPa). DFT calculations further explore the pressure-dependence of enthalpy differences, Raman modes, and band structures, providing insights into the structural and electronic transformations of BaV<small>₂</small>O<small>₆</small> under high pressure. This work deepens the understanding of the structural and band structure development of the metavanadate family under high pressure, contributing to advancements in material science under extreme conditions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"9 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793618","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":"Rocksalt-type heavy rare earth monoxides TbO, DyO, and ErO exhibiting metallic electronic states and ferromagnetism","authors":"Satoshi Sasaki, Daichi Oka, Daisuke Shiga, Ryunosuke Takahashi, Suguru Nakata, Koichi Harata, Yuichi Yamasaki, Miho Kitamura, Hironori Nakao, Hiroki Wadati, Hiroshi Kumigashira, Tomoteru Fukumura","doi":"10.1039/d4dt03214d","DOIUrl":"https://doi.org/10.1039/d4dt03214d","url":null,"abstract":"Solid-phase rare earth monoxides have been recently synthesized <em>via</em> thin film epitaxy. However, it has been difficult to synthesize heavy rare earth monoxides owing to their severe chemical instability. In this study, rocksalt-type heavy rare earth monoxides REOs (RE = Tb, Dy, Er) were synthesized for the first time, as single-phase epitaxial thin films. The REOs were characterized by hard X-ray photoemission spectroscopy, X-ray absorption spectroscopy, resonant photoemission spectroscopy, and magnetization measurements. These REOs showed metallic electronic states with the almost localized 4f states, indicating the 4f<small>^<em>n</em></small>5d<small>¹</small> electronic configurations of Tb, Dy, and Er ions. X-ray magnetic circular dichroism measurements of TbO evidenced the magnetic ordering of the 4f spins below the Curie temperature (<em>T</em><small>_C</small>). The <em>T</em><small>_C</small> was evaluated to be 233 K for TbO, 142 K for DyO, and 88 K for ErO, where the <em>T</em><small>_C</small> decreased with the 4f electron number, approximately proportional to the de Gennes factor.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"200 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793416","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}