Dalton Transactions最新文献

{"title":"In situ synthesis of a Bi2O3/Bi2S3 composite heterojunction for the electrochemical characterization of supercapacitors","authors":"Wenting Chen, Jiacheng Zheng, Yulong Deng, Chengliao Deng, Xiaoming Cai, Jinming Cai, Honglin Tan","doi":"10.1039/d5dt00026b","DOIUrl":"https://doi.org/10.1039/d5dt00026b","url":null,"abstract":"This study employs a two-step hydrothermal method to <em>in situ</em> introduce sulfur into a Bi<small>₂</small>O<small>₃</small> matrix. The synthesized material displays a specific capacitance of 305.57 F g<small>⁻¹</small> (2 A g<small>⁻¹</small>) and achieves a cycling stability of 94.12% (10 A g<small>⁻¹</small>), evidencing the enhancement of both capacitance and cycling stability attributed to the heterojunction. The existence of a built-in electric field was confirmed <em>via</em> theoretical calculations, highlighting the interactions between the electrode materials and ions. In addition, devices were constructed to demonstrate the practicality in real-world applications. This study proposes an effective methodology for the <em>in situ</em> synthesis of heterojunctions, offering fresh perspectives on the development of electrode materials for supercapacitors.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"89 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776132","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":"Hollow CoNiFe ternary metal selenide electrocatalysts derived from Prussian blue analogues for boosting the oxygen evolution reaction","authors":"Mingyang Cai, Weishun Song, Ziling Huang, Xiaoquan Yang, Junjie Fu, Lin Luo, Xueming Su, Hongwei Gu, Xueqin Cao","doi":"10.1039/d5dt00447k","DOIUrl":"https://doi.org/10.1039/d5dt00447k","url":null,"abstract":"The development of effective electrocatalysts is a top priority for the oxygen evolution reaction (OER), which is the crucial half-reaction of water electrolysis, since electrocatalytic water splitting for hydrogen production offers a practical solution to the upcoming energy crisis. Herein, we report a strategy to fabricate hollow ternary metal selenide (CoNiFe–Se) nanocubes derived from Prussian blue analogues (PBAs) by phytic acid etching and low-temperature gas-phase selenization. Due to the advantages of its multi-component composition and hollow structure, CoNiFe–Se exhibited a low overpotential of 275 mV@10 mA cm<small>⁻²</small>, a small Tafel slope of 62.3 mV dec<small>⁻¹</small> and a long-term stability of more than 80 h in 1.0 M KOH. This research offers an innovative idea and a straightforward technique for preparing hollow multimetallic selenide electrocatalysts derived from PBAs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776130","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":"Pb-Pd Alloy Catalysts with Intercalated Pb Atoms: Optimized Electronic and Lattice Structures for Enhanced Electrochemical Ethanol Oxidation","authors":"Yonghui Ye, Yu Zhang, Xintong Yan, Gong Ning, Shi Hu","doi":"10.1039/d5dt00117j","DOIUrl":"https://doi.org/10.1039/d5dt00117j","url":null,"abstract":"A facile one-step method is employed to synthesize carbon-supported Pd-Pb binary metal catalysts for the ethanol oxidation reaction (EOR) in alkaline electrolyte. A variety of characterization techniques have demonstrated that the alloying of Pd with Pb alters the electronic structure and induces lattice expansion. Electrochemical tests for EOR in alkaline electrolytes demonstrated that the Pd3Pb/C catalyst exhibited the highest mass activity (3.59 A·mgPd-1) and specific activity (17.97 mA·cm-²), which are 4.6 and 4.7 times that of the Pd/C catalyst prepared by the same method, respectively. The intercalation of lead atoms has altered both the lattice and the electronic structure of palladium, leading to opposing shifts in the d-band center that collectively optimize the adsorption strength of CO* and OH*, key intermediates of EOR. Consequently, the Pd3Pb/C electrocatalyst exhibits significant EOR catalytic activity. This study provides a viable implementation plan and analytical strategy to optimize palladium-based catalysts with non-noble metals by integrating explanations of electronic transfer, bifunctional effects, and d-band center adjustments for bimetallic catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776134","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":"Palladium(II) and Platinum(II) Complexes of Disubstituted Imidazo[1,5-a]Pyridine and Imidazolylpyridine: Coordination Chemistry, Versatile Catalysis, Biophysical Study","authors":"AMLAN RANJAN RAYASINGH, Vadivelu Manivannan","doi":"10.1039/d5dt00346f","DOIUrl":"https://doi.org/10.1039/d5dt00346f","url":null,"abstract":"Some pincer type mono- and poly-nuclear Pd(II) and Pt(II) complexes bearing imidazo[1,5-a]pyridine and imidazolylpyridine moiety were synthesized and characterized by using several spectroscopic methods. Determination of molecular structures of all complexes by single crystal X-ray diffraction studies revealed a distorted square planar geometry around the bivalent palladium and platinum in all complexes. These Pd(II) complexes have been observed to display high catalytic activity in various reaction such as Suzuki-Miyaura cross-coupling reaction, transfer hydrogenation reaction, and alkyne homocoupling. The theoretical study was also well matched with experimental data of all catalysts. Substantial deviations in the catalytic activity were observed by changing the co-ligand, binding mode of the ligand and the number of metal centre. Under optimal conditions, Suzuki cross-coupling and the transfer hydrogenation reaction were accomplished proficiently with wide functional group possibility by taking only 0.1 mol% of tetranuclear Pd(II) complex (5) as catalyst. Intermediates in Suzuki coupling reaction were also detected by using mass spectroscopy. Among all studied complexes, the tetra nuclear palladium complex exhibited high catalytic activity. Further Pd(II) complexes were tested in a model reaction of homocoupling of phenylacetylene and produce diphenylbutadiyne in excellent yield. Also, interaction study of all the complexes with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) were investigated using electronic spectroscopy Absorption study showed minor groove binding of DNA with these complexes while intercalative binding was observed by all complexes through displacement of ethidium bromide (EB) in EB-DNA by quenching of fluorescence intensity. The complexes were also displayed high binding affinity toward BSA confirmed by emission, synchronous fluorescence, and steady state fluorescence anisotropy measurement. Moreover, the pharmacokinetic properties of two bioactive compounds (3s and 3t) obtained from Suzuki coupling reaction were calculated and to evaluate their activity as leukotriene A4 hydrolase (LTA4H) inhibitor, these molecules were docked with human LTA4H enzyme.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"58 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776133","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":"Removal of dibenzothiophene by extraction and catalytic oxidation using long- and short-channel SBA-15 containing Zr and Mo species","authors":"Katarzyna Stawicka, Maciej Trejda, Aleksandra Rybka, Maria Ziolek","doi":"10.1039/d5dt00043b","DOIUrl":"https://doi.org/10.1039/d5dt00043b","url":null,"abstract":"Two different SBA-15 silicas with long and short channels, containing zirconium species, were prepared and used as supports for molybdenum additives. The resulting materials were characterized and tested as catalysts for extractive catalytic oxidative desulfurization (ECODS) of dibenzothiophene (DBT) using acetonitrile as a solvent and H<small>₂</small>O<small>₂</small> as an oxidant. The synthesis procedure for the zirconium-containing silicas influenced both the zirconium loading and its distribution, <em>i.e.</em>, whether it was incorporated into the framework or present in extra-framework positions. Additionally, the choice of support for molybdenum inclusion affected the amount of modifier loaded and its resistance to leaching, which collectively impacted the acidic and basic properties of the synthesized catalysts. The textural and surface properties of the materials were evaluated using low-temperature nitrogen adsorption/desorption, XRD, SEM-EDS, FT-IR-ATR, XPS, and UV-vis. The acidity and basicity of the samples were evaluated using FT-IR spectroscopy with pyridine adsorption/desorption and test reactions including 2-propanol dehydration/dehydrogenation and 2,5-hexanedione cyclization/dehydration. The catalytic activity was measured in ECODS. The Mo/ZrSBA-15-S catalyst demonstrated the best performance in DBT removal from the oil phase, achieving approximately 92% conversion of DBT within 120 minutes at 60 °C. This superior activity was attributed to the material's high acidity strength.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"197 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766572","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":"π−π Interactions Strategy for Targeting Highly Thermostable Bis(arylimino)pyridyliron Precatalysts in Ethylene Polymerization","authors":"Muhammad Zada, Qiuyue Zhang, Qaiser Mahmood, Yanping Ma, Yang Sun, Wen Hua Sun","doi":"10.1039/d5dt00571j","DOIUrl":"https://doi.org/10.1039/d5dt00571j","url":null,"abstract":"The suboptimal catalytic performance of bis(arylimino)pyridyliron precatalysts in ethylene polymerization at elevated temperatures remains a significant challenge. In this study, a series of six bis(arylimino)pyridyliron chloride precatalysts with incorporation of benzosuberyl steric bulk was prepared and investigated for ethylene polymerization. Capping the axial sites of the iron center with benzosuberyl steric bulk resulted in π−π interactions between the phenyl group and the chelate backbone, with a distance of ca. 3.293 Å for Fe3iPr, shorter than the sum of the van der Waals radii of carbon atoms (3.4 Å), as confirmed by single-crystal X-ray diffraction. These non-covalent interactions enhanced the thermal stability, catalytic activity, and polymer molecular weights. On activation with MAO or MMAO cocatalysts, these precatalysts exhibited the maximum activity of 2.53 × 10<small>⁷</small> g mol<small>^-1</small> h<small>^-1</small> at 80 <small>^o</small>C and 1.88 × 10<small>⁷</small> g mol<small>^-1</small> h<small>^-1</small> at 100 <small>^o</small>C, demonstrating their unprecedented thermal stability. The molecular weight of the produced polyethylene remained high, even at elevated temperatures. Moreover, ligand modifications had a pronounced impact on polymerization outcomes: the least sterically hindered complex, while producing comparatively lower molecular weight polyethylene, displayed higher activity and the most sterically hindered one showed opposite tendency. The molecular weight dispersity of polyethylene showed a strong correlation with the precatalyst structure and reaction conditions. High melting points confirmed the presence of strictly linear structures with high vinyl end groups (up to 74%), as verified by <small>¹</small>H/<small>¹³</small>C NMR spectra. A comparison of structurally related iron precatalysts emphasized significant improvements in both thermal stability and catalytic activity, attributed to the π−π interactions present in the current iron precatalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767019","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":"Graphitization of Tincone via Molecular Layer Deposition: Investigating Sulfur’s Role and Structural Impacts","authors":"Hyolim Jung, Hae LIn Yang, Gi-Beom Park, Ji-Min Kim, Jin-Seong Park","doi":"10.1039/d5dt00529a","DOIUrl":"https://doi.org/10.1039/d5dt00529a","url":null,"abstract":"This study investigated the synthesis of sp2 carbons using molecular layer deposition (MLD) with tincone, which utilized tetrakis(dimethylamido)tin (TDMASn) as the metal precursor and 4-mercaptophenol (4MP) as the organic linker. Tincone films were deposited at 100 °C without impurities and then subjected to vacuum post-annealing in a tube furnace to induce graphitization. Compositional and structural analyses revealed significant changes as the annealing temperature increased, including the breakdown of the bonds between Sn, O, S, and C . This process led to the reduction of Sn, O, and S and the formation of sp2 carbons. At 400 °C, the film thickness was reduced by 57.5%, and the refractive index increased from 1.8 to 1.97, as confirmed by the emergence of G-band and 2D-band peaks in the Raman spectra. X-ray photoelectron spectroscopy analysis indicated that the residual Sn content decreased to 0.75% at 600 °C. Interestingly, at temperatures above 400 °C, unique behavior was observed: increased C-S bonding disrupted the graphite structure due to the thiol (-SH) groups in 4MP. This disruption led to a reduction in C-C bonding and a decrease in the G-band peak in the Raman spectra. This study provides the first detailed investigation of the role of S in the graphitization of tincone, highlighting its impact on sp2 carbon formation and emphasizing the importance of the careful selection of precursors and linkers in MLD processes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776180","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":"Optimizing energy levels in perovskite solar cells with dual hole and dual electron transport layers","authors":"Wenfeng Liu, Jicheng Zhou, Hua Yang, Zhiyong Chen, Zao Yi","doi":"10.1039/d5dt00463b","DOIUrl":"https://doi.org/10.1039/d5dt00463b","url":null,"abstract":"This study presents a high-efficiency solar cell featuring dual hole transport layers (HTL) and dual electron transport layers (ETL), with a structure of ITO/ZnO/CDS/CH3NH3PbI3/Se-Te: Cu2O/NiO/Al. The combination of ZnO/CDS as dual ETL and Se-Te: Cu2O/NiO as dual HTL optimizes carrier transport and collection efficiency. Simulations based on the Poisson equation and carrier continuity equations demonstrate that this design significantly reduces interfacial recombination losses and improves band alignment. As a result, the cell achieves a fill factor (FF) of 84.04 %, a short-circuit current density (Jsc) of 21.39 mA/cm², and a power conversion efficiency (PCE) of 20.14 %. The research highlights the critical role of the dual transport layer structure in enhancing carrier separation and transport efficiency, providing valuable theoretical and experimental insights for the design and optimization of future high-performance solar cells.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766583","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":"Synthesis, Structure, Spectral and Redox Properties of 3-Pyrrolyl BODIPYs Containing One to Eight Bromides at the Pyrrole Carbons","authors":"Pinky Chauhan, Mangalampalli Ravikanth","doi":"10.1039/d5dt00431d","DOIUrl":"https://doi.org/10.1039/d5dt00431d","url":null,"abstract":"We report regioselective bromination of meso-aryl 3-pyrrolyl BODIPY by introducing one to eight bromides at the pyrrole carbons of three pyrrole rings by treating meso-aryl 3-pyrrolyl BODIPY with N-bromosuccinimide/Br2 in CH2Cl2 under mild reaction conditions. The crystal structures obtained for five of these pyrrole brominated meso-aryl 3-pyrrolyl BODIPYs indicated that the appended pyrrolyl group adopts distortion from the 12-atom mean plane of the BODIPY and the maximum distortion of 40° was observed for octabrominated meso-aryl 3-pyrrolyl BODIPY. Upon increase of number of bromides from one to eight at the pyrrole carbons of meso-aryl 3-pyrrolyl BODIPY, the following key observations were made: (i) the absorption bands experiences bathochromic shift upto introduction of five bromides followed by hypsochromic shift from six to eight bromides indicating that the magnitude of absorption band shifts are non-additive; (ii) the fluorescence band experienced bathochromic shifts along with the decrease of quantum yield and singlet state lifetime; (iii) the electrochemical studies indicated that brominated 3-pyrrolyl BODIPYs are electron deficient and undergoes easier reductions with the increase of number of bromides at the pyrrole carbons of 3-pyrrolyl BODIPY. A linear additive relationship was noted between E1/2red and number of bromide groups at the pyrrole carbons of 3-pyrrolyl BODIPY and (iv) the halogenated 3-pyrrolyl BODIPYs are very efficient in generating singlet oxygen and the linear relationship was observed between singlet oxygen quantum yields and the number of bromides at the pyrrole carbons of 3-pyrrolyl BODIPY. DFT and TD-DFT studies supports the experimental observations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"20 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766582","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":"Insight into the pressure-engineered structure-property relationship of organic-inorganic hybrid perovskites through high-throughput first-principles calculations","authors":"Ling-Jun He, Huan-Huan Yang, Wen-Yong Lai","doi":"10.1039/d5dt00365b","DOIUrl":"https://doi.org/10.1039/d5dt00365b","url":null,"abstract":"Searching for novel organic-inorganic hybrid perovskite materials with long-term stability and excellent optoelectronic properties is the focus of optoelectronic field. High-pressure as a special thermodynamic parameter, offers a promising avenue for discovering and designing materials with optimized performance. However, the data-driven pressure-engineered structure-property relationships remains scarce, leading to an insufficiently understanding of the physical rules by which pressure regulation influences the microstructure and electronic properties of materials. In this study, we conduct high-throughput first-principles calculation to construct a database of hundreds of cubic ABX3 candidates and evaluate their property evolutions under pressures ranging from 0 to 10 GPa. Through systematic assessments of the crystallographic stability, thermodynamic stability, and electronic properties, we obtain the following findings: the B-site metal predominantly determines crystal structure stability; the X-site halogen governs thermodynamic stability; and the ionic radius of A-site organic cation plays a pivotal role in modulating the electronic properties. Based on extensive theoretical calculations, this study confirms the influence of “single-component” effect, further enriching the existing knowledge that the synergistic changes in bond length or bond angle between B-site and X-site under pressure are the main factors affecting material properties. The insights derived from current analysis provide a valuable foundation for rational design of the optimized OIHP materials under pressure.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"16 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776135","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}