Chemical Science最新文献

{"title":"Fluorine-mediated single-step ethylene purification in face-transitive metal-organic frameworks from binary to ternary gas mixtures","authors":"Wei-Hong Zhang, Ya-Nan Ma, Guo-Tong Du, Ping Wang, Dong-Xu Xue","doi":"10.1039/d5sc06836c","DOIUrl":"https://doi.org/10.1039/d5sc06836c","url":null,"abstract":"Ethylene is a pivotal feedstock for the chemical industry. Obtaining polymer-grade ethylene in a single step from either binary ethane/ethylene or ternary acetylene/ethane/ethylene mixtures via porous adsorbents is highly energy-efficient yet remains a formidable challenge. Face-transitive topologies, a particular class of nets in reticular chemistry, possess only one window type and thus hold exceptional promise for discriminating between closely related C₂ hydrocarbons. Guided by the <strong>nia-d</strong> topology, we synthesized two isoreticular, trinuclear-manganese-cluster-based, ternary metal–organic frameworks (MOFs), namely <strong>nia-d</strong>-TZB and <strong>nia-d</strong>-FTZB, under solvothermal conditions using MnCl₂, the tritopic linker 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT), and the heterofunctional linear linkers 4-(1H-tetrazol-5-yl) benzoic acid (H<small>₂</small>TZB) or 2-fluoro-4-(1H-tetrazol-5-yl)benzoic acid (H<small>₂</small>FTZB). Although the resultant trigonal-bipyramidal cages remain dimensionally invariant, the introduction of fluorine in the latter linker subtly reduces the size of the antiprismatic cages and the sole triangular window in <strong>nia-d</strong>-FTZB. Single-component adsorption isotherms reveal that <strong>nia-d</strong>-TZB preferentially adsorbs ethane, whereas <strong>nia-d</strong>-FTZB preferentially adsorbs both acetylene and ethane. Consequently, <strong>nia-d</strong>-TZB enables one-step purification of ethylene from an ethane/ethylene mixture, while <strong>nia-d</strong>-FTZB achieves simultaneous removal of acetylene and ethane from an acetylene/ethane/ethylene ternary stream, again delivering polymer-grade ethylene in a single pass. These findings are corrob­orated by ideal adsorbed solution theory (IAST), breakthrough experiments with both binary and ternary gas mixtures, and detailed theoretical simulations. This study furnishes compelling evidence for the rational design of face-transitive MOFs to tackle complex gas-separation tasks.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Achieving Ultra-low Oxygen Transport Resistance of Fuel Cell by Microporous Covalent Organic Framework Ionomers","authors":"Xiaoqin Ma, Xiaoli Lu, Shimei Liang, Caili Yuan, Jingtao Si, Jianchuan Wang, Zidong Wei","doi":"10.1039/d5sc04070a","DOIUrl":"https://doi.org/10.1039/d5sc04070a","url":null,"abstract":"Research on ultra-low platinum (Pt)-loaded fuel cells is essential for reducing costs and advancing hydrogen fuel cell commercialization. However, oxygen diffusion resistance remains a major challenge, limiting the oxygen reduction reaction (ORR) and fuel cell efficiency. To address this challenge, a stable colloidal dispersion of polymer-grafted Covalent Organic Frameworks (COFs) ionomers have been developed. These COF ionomers enhance hydroxide conductivity and oxygen transport by creating a sub-nm porous structure on the catalyst surface, while also dispersing catalyst particles and stabilizing the three-phase interface. Compared to polymer electrodes, COF ionomer electrodes reduce oxygen transport resistance by 96.4%. With ultra-low Pt loading (60 μg cm⁻²), COF ionomer electrodes achieve a peak power density of 0.78 W cm⁻², 3 times higher than polymer electrodes. This study presents a promising alternative for the development of more efficient ionomers with low oxygen transfer resistance in fuel cells.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Novel Metallo-Supramolecular Architectures Based on Side-Pyridine-Modified Terpyridines: Design, Self-assembly, and Properties","authors":"Ningxu Han, Xin Jiang, Ming Wang","doi":"10.1039/d5sc06054k","DOIUrl":"https://doi.org/10.1039/d5sc06054k","url":null,"abstract":"2,2':6',2''-terpyridine (tpy), as a classical tridentate chelating ligand, has been extensively utilized to construct discrete metallo-supramolecular architectures. However, current research has predominantly focused on conventional modification strategies at the 4'-position of the central pyridine ring. Recent breakthroughs in synthetic methodologies for side-pyridine functionalization have given rise to a new generation of tpy-based metallo-supramolecular systems. These innovative achievements have transcended the limitations of traditional design paradigms by significantly improving the coordination selectivity of terpyridine systems, thereby substantially expanding both the structural diversity and functional dimensionality of tpy-based coordination chemistry. This review systematically summarizes recent advances in novel side-pyridine-modified tpy-based coordination supramolecular architectures, including mononuclear complexes, helicates, two-dimensional (2D) macrocycles and polygons, three-dimensional (3D) cages and polyhedra, and decker architectures. A comprehensive discussion is provided on the functional implementations of these systems across various domains, particularly highlighting their applications in luminescence, catalysis, chirality, host-guest chemistry, and hierarchical self-assembly.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"63 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"eCarbonyls: an electrochemical thioether mediated oxidation of alcohols to aldehydes and ketones","authors":"Conall Molloy, Simon Kaltenberger, Lee Edwards, Katherine M. P. Wheelhouse, Kevin Lam","doi":"10.1039/d5sc06546a","DOIUrl":"https://doi.org/10.1039/d5sc06546a","url":null,"abstract":"We report eCarbonyls, a scalable, metal-free electrochemical oxidation of alcohols that mimics key features of the classical Swern reaction while avoiding its reliance on cryogenic conditions and hazardous reagents. Operating at room temperature in an undivided cell, this process employs a stable thioether mediator to generate reactive radical cation intermediates that enable selective oxidation of primary and secondary alcohols to aldehydes and ketones. The method displays broad substrate scope, with up to 98% isolated yields across more than 25 examples, and excellent tolerance toward sensitive functional groups, including azides, boronates, and silyl ethers. Mechanistic studies confirm the role of anodically generated thioether radical cations and highlight the importance of the external base. Notably, eCarbonyls is readily scalable and adaptable to flow electrolysis, enabling multigram synthesis and offering a safe, sustainable platform for academic and industrial applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"86 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Click-Assembled N-Graphene-C60 Hybrids for Ultrafast Electron Transfer","authors":"Luis Miguel Arellano Castellanos, Habtom B. Gobeze, Youngwoo B. Jang, Maria J Gómez-Escalonilla, Paul Karr, Francis D'Souza, Fernando Langa","doi":"10.1039/d5sc06142c","DOIUrl":"https://doi.org/10.1039/d5sc06142c","url":null,"abstract":"A novel donor-acceptor hybrid derived from N-doped graphene (NG) and an electron acceptor, C 60<small></small> , has been newly synthesized using click chemistry and characterized by a suite of physico-chemical techniques. The usage of click chemistry resulted in a relatively high degree of functionalization. Due to the presence of two C₁₂ alkyl chains on the fulleropyrrolidine moiety, the NG-C 60<small></small> hybrid was found to be relatively soluble in most organic solvents, facilitating both spectroscopic and electrochemical characterization.Fluorescence studies revealed quenching of the fulleropyrrolidine emission, indicating the occurrence of excited-state events. While DFT studies provided insights into the geometry and localization of the frontier orbitals, the TD-DFT studies performed at the B3LYP/6-311G(d,p) level suggested the possibility of excited-state charge transfer from several excited states. Subsequent femtosecond transient absorption studies performed in DMF confirmed electron transfer, wherein the material could be characterized. The charge transfer state persisted for approximately 12 ps before populating the low-lying 3 C <small>₆₀</small> *, highlighting the material's potential for light energy harvesting applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Illumination-induced deep trap state activation at the nanocluster/TiO2 interface: the origin of intrinsic photocapacitance in sensitized solar cells","authors":"Muhammad A. Abbas, Raju Thota, Minwook Jeon, Jin Ho Bang","doi":"10.1039/d5sc04085j","DOIUrl":"https://doi.org/10.1039/d5sc04085j","url":null,"abstract":"Noble metal nanoclusters (NCs) in photoelectrochemical systems reveal novel functionalities. This study unveils that metal nanocluster-sensitized solar cells (MCSSCs) can intrinsically function as photocapacitors, storing charge in the dark. Illumination of Au<small>₂₂</small>(SG)<small>₁₈</small> NC-sensitized TiO<small>₂</small> activates deep surface trap states, forming an interfacial capacitance responsible for a persistent dark built-in potential. Open-circuit voltage decay experiments demonstrate a stable dark voltage post-illumination, a phenomenon absent in applied-bias voltage decay experiments, highlighting the crucial role of photogenerated holes within NCs in charging this capacitor. A proposed model features TiO<small>₂</small> deep traps as the negative electrode, glutathione ligands as the dielectric, and the NC core (hosting holes) as the positive electrode. This intrinsic photocapacitive behavior, achieved without external storage components, is unprecedented in sensitized solar cells. These findings offer profound insights into NC/TiO<small>₂</small> interfacial dynamics and suggest MCSSCs as candidates for integrated solar energy conversion and storage, paving the way for novel photocapacitor designs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"8 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229031","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A tetraazanaphthalene radical-bridged dysprosium single-molecule magnet with a large coercive field","authors":"Florian Benner, Saroshan Deshapriya, Selvan Demir","doi":"10.1039/d5sc05358g","DOIUrl":"https://doi.org/10.1039/d5sc05358g","url":null,"abstract":"Generating strong magnetic coupling poses a fundamental challenge in the design of multinuclear lanthanide complexes. The inherently contracted nature of the valence 4f orbitals precludes the lanthanides from engaging in covalent bonding with closed-shell ligands. The employment of open-shell bridging ligands instead allows efficient interaction of the diffuse radical spin orbitals with the 4f shell of the lanthanides. Herein, we introduce the azaacene ligand, 1,4,5,8-tetraazanaphthalene (tan), into rare earth chemistry: first, we synthesized [(Cp*<small>₂</small>Dy)<small>₂</small>(μ-tan)] (<strong>1</strong>, Cp* = pentamethylcyclopentadienyl) containing a diamagnetic tan<small>²⁻</small> bridge from a salt metathesis reaction of Cp*<small>₂</small>DyBPh<small>₄</small> and K<small>₂</small>(tan). Second, we chemically oxidised <strong>1</strong> to [(Cp*<small>₂</small>Dy)<small>₂</small>(μ-tan˙)][BArF<small>₂₀</small>] (<strong>2</strong>) comprising a tan<small>¹⁻</small>˙ radical bridge. <strong>2</strong> is a rare radical-bridged single-molecule magnet (SMM) with open hysteresis loops below 3.75 K with a maximum coercive field (<em>H</em><small>_C</small>) of 1.373 T at 1.8 K, which represents a notable record as <em>H</em><small>_C</small> is approximately doubled compared to all known dinuclear lanthanide SMMs innate to organic radical bridges. A close match of the tan<small>¹⁻</small>˙/tan<small>²⁻</small> and Dy<small>^III</small>/Dy<small>^II</small> redox potentials may be the origin for the impressive hysteresis loops at low temperatures, while the magnetic behaviour at higher temperatures is likely impacted from spin–phonon coupling. The outlined design strategy of matching reduction potentials of the ligand with the metal ions to amplify magnetic coupling, was proposed <em>via</em> prior computations, but is within this study for the first time experimentally confirmed. In sum, highly-tunable azaacene radicals have immense potential not only for radical-containing SMMs but for high-performance magnetic materials at large.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"39 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Probing Supramolecular Structures in Solution by Resonant Energy Transfer in the X-ray range","authors":"Viola Caroline C D'Mello, V. Rao Mundlapati, Jeremy DONON, Valerie Brenner, Michel Mons, Denis CEOLIN, Eric Gloaguen","doi":"10.1039/d5sc05911a","DOIUrl":"https://doi.org/10.1039/d5sc05911a","url":null,"abstract":"Supramolecular structures in solution are probed using Far-Zone Resonant Energy Transfer (FZRET) in an aqueous potassium acetate microjet. This advanced X-ray spectroscopic technique relies on the resonant energy transfer between donor atoms, i.e. core-ionised potassium ions, and acceptor atoms a few nm away. These experiments reveal an inhomogeneous distribution of ions in water, and are consistent with the presence of nm-sized ionic clusters at 4.1 M concentration.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Accelerating N2H4(ads) formation by frustrated Lewis pairs in oxyhydroxide for electrocatalytic ammonia oxidation into N2","authors":"Meng-Ying Yin, Xing-Yuan Xia, Ting Dai, Xia Chen, Qiu-Ju Xing, Lei Tian, Jian-Ping Zou","doi":"10.1039/d5sc06524k","DOIUrl":"https://doi.org/10.1039/d5sc06524k","url":null,"abstract":"Conventional catalysts based on individual Oswin and Salomon (O-S) or Gerischer and Mauerer (G-M) mechanism cannot achieve direct electrocatalytic ammonia (NH3) oxidation into nitrogen (N2) with high activity and selectivity. Herein, a bimetallic nickel-cobalt oxyhydroxide (Ni0.5-Co0.5-OOH) with frustrated Lewis pairs was developed through an elaborate analysis of the binding types of NH3 with metal-oxide anode, efficiently integrating O-S and G-M mechanisms for converting NH3 into N2 with high activity (94%) and selectivity (63%), which is much superior to the anodes in the previous reports. The evidence of batch experiments, in-situ characterizations, and theoretical calculations confirms that two NH3 molecules bind to Co3+ sites (Lewis acid) in CoOOH and hydroxy sites (Lewis base) in NiOOH, respectively. Then, the NH2(ads) generated on the Lewis acid sites can quickly recombine with the NH2(ads) desorbed from the Lewis base sites, accelerating the formation of N2H4(ads) and preventing the peroxidation of NH3. The electrocatalytic system assembled with Ni0.5-Co0.5-OOH anode shows excellent performance for NH3 elimination in secondary aerobic process effluent. Our work provides precious guidance for the design of novel anodes and sheds light on further promoting the performance of ammonia conversion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"197 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Voltage- and pH-Driven Evolution of Multi-Pathway C-C Coupling in CO2 Electroreduction on Copper","authors":"Chengyi Zhang, Ziyun Wang","doi":"10.1039/d5sc05367f","DOIUrl":"https://doi.org/10.1039/d5sc05367f","url":null,"abstract":"Reducing CO2 into high-energy-density multi-carbon products is critical for addressing climate and energy challenges, with copper being the only metal capable of catalyzing this transformation. However, the fundamental mechanisms of C-C coupling on copper surfaces remain elusive. Previous models have primarily focused on *OC-CO and *OC-COH coupling steps, lacking the dynamic and comprehensive perspective towards the whole system. Addressing this gap, our microkinetic modeling systematically investigates how environmental factors modulate multi-pathway C-C coupling mechanisms. We demonstrate that voltage and pH do not simply enhance a single coupling step but dynamically regulate the accessibility and competition among multiple coupling routes, consistent with previous experimental research. These findings establish a more comprehensive understanding of C-C coupling under realistic electrochemical conditions, offering new guidance for the rational design and optimization of copper-based catalysts for sustainable multi-carbon product synthesis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229028","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}