Yi-An Zhao, Ge Sun, Heng Jiang, Zhixuan Wei, Fei Du
Anode-free solid-state sodium batteries (AFSSBs) represent a transformative paradigm, positioning themselves as the ultimate avenue to unlock the high-energy-density potential of sodium-based electrochemistry. However, their practical implementation is hindered by fundamental challenges, including inadequate solid electrolyte properties, unstable interfacial contacts, and uncontrolled sodium deposition morphology. This review provides a timely and systematic analysis of this evolving frontier. Following a clear presentation of the existing challenges, we organize and discuss emerging strategies spanning three key areas: the development of novel electrolytes, the construction of stable interfaces, and the optimization of current collector substrates. The pivotal role of advanced characterization in elucidating underlying mechanisms is also underscored. In the final section, we outline a forward-looking roadmap, identifying critical research pathways to accelerate the translation of AFSSB technology from promising prototypes toward practical, next-generation energy storage solutions.
{"title":"Anode-Free Solid-State Sodium Batteries: Navigating the Challenges toward High Energy Density","authors":"Yi-An Zhao, Ge Sun, Heng Jiang, Zhixuan Wei, Fei Du","doi":"10.1039/d6sc00853d","DOIUrl":"https://doi.org/10.1039/d6sc00853d","url":null,"abstract":"Anode-free solid-state sodium batteries (AFSSBs) represent a transformative paradigm, positioning themselves as the ultimate avenue to unlock the high-energy-density potential of sodium-based electrochemistry. However, their practical implementation is hindered by fundamental challenges, including inadequate solid electrolyte properties, unstable interfacial contacts, and uncontrolled sodium deposition morphology. This review provides a timely and systematic analysis of this evolving frontier. Following a clear presentation of the existing challenges, we organize and discuss emerging strategies spanning three key areas: the development of novel electrolytes, the construction of stable interfaces, and the optimization of current collector substrates. The pivotal role of advanced characterization in elucidating underlying mechanisms is also underscored. In the final section, we outline a forward-looking roadmap, identifying critical research pathways to accelerate the translation of AFSSB technology from promising prototypes toward practical, next-generation energy storage solutions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"13 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490099","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}
The development of PFAS-free fluorinated scaffolds that preserve the desirable physicochemical attributes of perfluoroalkyl groups remains a central challenge in contemporary fluorine chemistry. Herein, we report a rapid and bidirectional skeletal-remodelling platform that enables controlled interconversion between aromatic, medium-sized, and bicyclic SF5-containing heterocycles from readily accessible SF5-nitrobenzenes. Phosphorus-catalyzed iterative deoxygenation of SF5-nitrobenzenes generates arylnitrene intermediates that undergo remarkably accelerated dearomative ring expansion, furnishing seven-membered SF5-azepines within dramatically shortened reaction times compared to non-SF5 analogues. These azepines function as versatile skeletal nodes, enabling divergent downstream transformations: photoinduced 4π-electrocyclization provides access to previously unexplored SF5-azabicyclo[3.2.0]hepta-2,6-diene frameworks, while selective fluoroacylative activation promotes reverse skeletal reconstruction to restore aromaticity and deliver SF5-substituted benzimidazoles. Collectively, this work demonstrates that strategic incorporation of the SF5 group not only expands accessible heterocyclic architectures but also fundamentally alters skeletal rearrangement kinetics, enabling rapid and controllable skeletal editing from a common, practical precursor. Given the OECD classification of SF5-containing molecules as non-PFAS, this unified skeletal-remodelling approach substantially broadens the design space of fluorinated scaffolds for applications in pharmaceuticals, agrochemicals, and functional materials, advancing the principles of sustainable fluorine chemistry.
{"title":"Bidirectional skeletal remodelling of SF 5 -nitrobenzenes into azepine, bicyclic, and benzimidazole frameworks","authors":"Muhamad Zulfaqar Bacho, Shiwei Wu, Takuya Muramatsu, Chavakula Nagababu, Daiki Harano, Seishu Ochiai, Norio Shibata","doi":"10.1039/d6sc01441k","DOIUrl":"https://doi.org/10.1039/d6sc01441k","url":null,"abstract":"The development of PFAS-free fluorinated scaffolds that preserve the desirable physicochemical attributes of perfluoroalkyl groups remains a central challenge in contemporary fluorine chemistry. Herein, we report a rapid and bidirectional skeletal-remodelling platform that enables controlled interconversion between aromatic, medium-sized, and bicyclic SF5-containing heterocycles from readily accessible SF5-nitrobenzenes. Phosphorus-catalyzed iterative deoxygenation of SF5-nitrobenzenes generates arylnitrene intermediates that undergo remarkably accelerated dearomative ring expansion, furnishing seven-membered SF5-azepines within dramatically shortened reaction times compared to non-SF5 analogues. These azepines function as versatile skeletal nodes, enabling divergent downstream transformations: photoinduced 4π-electrocyclization provides access to previously unexplored SF5-azabicyclo[3.2.0]hepta-2,6-diene frameworks, while selective fluoroacylative activation promotes reverse skeletal reconstruction to restore aromaticity and deliver SF5-substituted benzimidazoles. Collectively, this work demonstrates that strategic incorporation of the SF5 group not only expands accessible heterocyclic architectures but also fundamentally alters skeletal rearrangement kinetics, enabling rapid and controllable skeletal editing from a common, practical precursor. Given the OECD classification of SF5-containing molecules as non-PFAS, this unified skeletal-remodelling approach substantially broadens the design space of fluorinated scaffolds for applications in pharmaceuticals, agrochemicals, and functional materials, advancing the principles of sustainable fluorine chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490096","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}
Yuanyong Huang, Cai Ning, Xinyu Lu, Yang Chao, Junhao He, Qiankun Gao, Yu Yu, Zhongkai Xie, Hailing Huo, Weidong Shi
Conventional photocatalysts are inherently inefficient at harnessing the predominant near-infrared (NIR) component of sunlight, and intrinsic kinetic and thermodynamic barriers further impose a severe constraint on solar-to-hydrogen (H2) conversion efficiency. However, the rational design of highly efficient, durable NIR-responsive photocatalysts that avoid scarce metal cocatalysts and toxic dyes remains a pivotal challenge. Herein, we demonstrate a new strategy for constructing a strong interfacial coupled heterojunction that strategically integrates plasmonic CuSe with S-vacancy-rich ZnIn2S4 (Vs-ZnIn2S4) to enhance NIR-driven H2 evolution through a plasmon-mediated dual excitation (PMDE) mechanism. As evidenced by ultrafast femtosecond transient absorption (fs-TA) spectroscopy and density functional theory (DFT) calculations, the rational heterointerface engineering builds fast charge-transfer channels, which in turn lower the reaction energy barrier, suppress carrier recombination, and induce interfacial charge redistribution. These improvements collectively contribute to an optimized heterojunction that achieves an apparent quantum efficiency of 3.0% at 940 nm, surpassing all state-of-the art noble-metal-free photocatalysts operating beyond 900 nm reported to date. The composite maintains its structural and catalytic integrity even under strong acidic/alkaline conditions (e.g., pH = 1 and pH = 12) and in high-salinity environments (e.g., 5.0 M NaCl solution), setting a benchmark for ultrastable NIR light-harvesting photocatalysts. This work provides novel insights into optimizing charge separation, stabilization, and accumulation during NIR-driven H2 production via PMDE.
传统的光催化剂在利用太阳光中主要的近红外（NIR）成分方面效率低下，而且内在的动力学和热力学障碍进一步严重限制了太阳能到氢（H2）的转换效率。然而，合理设计高效、耐用的nir响应光催化剂，避免稀有金属助催化剂和有毒染料仍然是一个关键的挑战。在此，我们展示了一种构建强界面耦合异质结的新策略，该策略将等离子体CuSe与富含s空位的ZnIn2S4 （Vs-ZnIn2S4）战略性地集成在一起，通过等离子体介导的双激发（PMDE）机制增强nir驱动的H2演化。超快飞秒瞬态吸收（fs-TA）光谱和密度泛函数理论（DFT）计算表明，合理的异质界面工程构建了快速电荷转移通道，从而降低反应能垒，抑制载流子复合，诱导界面电荷重新分布。这些改进共同促成了优化的异质结，在940 nm处实现了3.0%的表观量子效率，超过了迄今为止报道的所有900 nm以上的无贵金属光催化剂。即使在强酸/强碱条件下（如pH = 1和pH = 12）和高盐度环境下（如5.0 M NaCl溶液），该复合材料也能保持其结构和催化完整性，为超稳定的近红外捕光催化剂树立了标杆。这项工作为通过PMDE优化nir驱动制氢过程中的电荷分离、稳定和积累提供了新的见解。
{"title":"Constructing Interfacial Charge Transfer Channels via Plasmon Mediated Dual Excitation in S-Vacancy-Rich ZnIn2S4/CuSe Heterostructures for Enhanced NIR-Driven H2 Production","authors":"Yuanyong Huang, Cai Ning, Xinyu Lu, Yang Chao, Junhao He, Qiankun Gao, Yu Yu, Zhongkai Xie, Hailing Huo, Weidong Shi","doi":"10.1039/d6sc01125j","DOIUrl":"https://doi.org/10.1039/d6sc01125j","url":null,"abstract":"Conventional photocatalysts are inherently inefficient at harnessing the predominant near-infrared (NIR) component of sunlight, and intrinsic kinetic and thermodynamic barriers further impose a severe constraint on solar-to-hydrogen (H2) conversion efficiency. However, the rational design of highly efficient, durable NIR-responsive photocatalysts that avoid scarce metal cocatalysts and toxic dyes remains a pivotal challenge. Herein, we demonstrate a new strategy for constructing a strong interfacial coupled heterojunction that strategically integrates plasmonic CuSe with S-vacancy-rich ZnIn2S4 (Vs-ZnIn2S4) to enhance NIR-driven H2 evolution through a plasmon-mediated dual excitation (PMDE) mechanism. As evidenced by ultrafast femtosecond transient absorption (fs-TA) spectroscopy and density functional theory (DFT) calculations, the rational heterointerface engineering builds fast charge-transfer channels, which in turn lower the reaction energy barrier, suppress carrier recombination, and induce interfacial charge redistribution. These improvements collectively contribute to an optimized heterojunction that achieves an apparent quantum efficiency of 3.0% at 940 nm, surpassing all state-of-the art noble-metal-free photocatalysts operating beyond 900 nm reported to date. The composite maintains its structural and catalytic integrity even under strong acidic/alkaline conditions (e.g., pH = 1 and pH = 12) and in high-salinity environments (e.g., 5.0 M NaCl solution), setting a benchmark for ultrastable NIR light-harvesting photocatalysts. This work provides novel insights into optimizing charge separation, stabilization, and accumulation during NIR-driven H2 production via PMDE.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147496392","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}
Sergi Ruiz-Barragan, Daniel Muñoz, Saskia Körning, Dominik Marx
Although nanofluidics and chemistry in nanoconfined liquids has emerged as an exciting field, the quantitative impact of confinement on fundamental properties remains often unclear. Currently, there is not yet consensus on the impact of slit pore confinement on water self-dissociation, namely if this ubiquitous elementary reaction is enhanced, unaltered or suppressed by nanoconfinement. We address this question for well-defined water/graphene slit pore systems that allow us to carefully establish the appropriate thermodynamic conditions for different pore fillings. Anticipating our key results, we show that the energetics of the self-dissociation reaction is very sensitive to even subtle changes of the confinement conditions, leading even to non-monotonic behavior depending on water filling. This effect is found to correlate with the different capabilities of different nanoconfined water lamellae to solvate the nascent hydroxide defect beyond its second hydration shell parallel to the confining walls.
{"title":"Water self-dissociation in slit pores displays non-monotonic behavior as a function of water filling","authors":"Sergi Ruiz-Barragan, Daniel Muñoz, Saskia Körning, Dominik Marx","doi":"10.1039/d5sc07909h","DOIUrl":"https://doi.org/10.1039/d5sc07909h","url":null,"abstract":"Although nanofluidics and chemistry in nanoconfined liquids has emerged as an exciting field, the quantitative impact of confinement on fundamental properties remains often unclear. Currently, there is not yet consensus on the impact of slit pore confinement on water self-dissociation, namely if this ubiquitous elementary reaction is enhanced, unaltered or suppressed by nanoconfinement. We address this question for well-defined water/graphene slit pore systems that allow us to carefully establish the appropriate thermodynamic conditions for different pore fillings. Anticipating our key results, we show that the energetics of the self-dissociation reaction is very sensitive to even subtle changes of the confinement conditions, leading even to non-monotonic behavior depending on water filling. This effect is found to correlate with the different capabilities of different nanoconfined water lamellae to solvate the nascent hydroxide defect beyond its second hydration shell parallel to the confining walls.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"27 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478928","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}
Huizhe Wang, Huijia Liu, Wenqing Li, Shuai Li, Jiaqi Zhang, Jingzhe Zang, Li Liu, Peng Wang
Retraction of ‘Supramolecular engineering cascade regulates NIR-II J-aggregates to improve photodynamic therapy’ by Huizhe Wang et al., Chem. Sci., 2024, 15, 11347–11357, https://doi.org/10.1039/D4SC03020F.
Min-Jong Bong, Wonjung Lee, Daehan Lee, Hyunuk Kim, Junhyeok Seo, Ho-Jin Son
The selective formation of metal–hydride intermediates represents a key mechanistic step in Mn-based CO2 reduction catalysis, yet remains kinetically challenging. Herein, we report the discovery of a secondary-sphere proton channel that markedly accelerates Mn–H formation in visible-light-driven CO2-to-formate conversion. Mn(I) bipyridyl complexes bearing ethylene-bridged Brønsted acidic and basic pendants at the 6,6′-positions of the ligand establish a dynamic hydrogen-bond network that relays protons from protonated triethanolamine (TEOA(H)) directly to the metal center. Operando FTIR and DFT analyses reveal that this bio-inspired secondary coordination sphere (SCS) mimics the proton-transfer architecture of formate dehydrogenase (FDH), lowering the activation barrier for hydride formation while suppressing Mn–Mn dimerization. The optimized Mn-bpydiOMe complex delivers a turnover number of ~300 with >94% formate selectivity—performance that ranks among the best for Mn-based molecular systems—and, notably, achieves a solar-to-fuel quantum yield of 25.9% for the reducing half reaction in the presence of sacrificial electron donors, highlighting the remarkable efficiency gained from SCS-assisted proton delivery. These findings demonstrate that strategic SCS engineering can emulate enzymatic proton channels, enabling precise control over hydride chemistry and guiding Mn-catalyzed CO2 reduction exclusively toward formate formation.
{"title":"A Secondary-Sphere Proton Channel Accelerating Metal–Hydride Formation in Mn(I) Catalysts for Selective CO2-to-Formate Conversion","authors":"Min-Jong Bong, Wonjung Lee, Daehan Lee, Hyunuk Kim, Junhyeok Seo, Ho-Jin Son","doi":"10.1039/d5sc09412g","DOIUrl":"https://doi.org/10.1039/d5sc09412g","url":null,"abstract":"The selective formation of metal–hydride intermediates represents a key mechanistic step in Mn-based CO<small><sub>2</sub></small> reduction catalysis, yet remains kinetically challenging. Herein, we report the discovery of a secondary-sphere proton channel that markedly accelerates Mn–H formation in visible-light-driven CO<small><sub>2</sub></small>-to-formate conversion. Mn(I) bipyridyl complexes bearing ethylene-bridged Brønsted acidic and basic pendants at the 6,6′-positions of the ligand establish a dynamic hydrogen-bond network that relays protons from protonated triethanolamine (TEOA(H)) directly to the metal center. Operando FTIR and DFT analyses reveal that this bio-inspired secondary coordination sphere (SCS) mimics the proton-transfer architecture of formate dehydrogenase (FDH), lowering the activation barrier for hydride formation while suppressing Mn–Mn dimerization. The optimized <strong>Mn-bpy</strong><small><sup><strong>diOMe</strong></sup></small> complex delivers a turnover number of ~300 with >94% formate selectivity—performance that ranks among the best for Mn-based molecular systems—and, notably, achieves a solar-to-fuel quantum yield of 25.9% for the reducing half reaction in the presence of sacrificial electron donors, highlighting the remarkable efficiency gained from SCS-assisted proton delivery. These findings demonstrate that strategic SCS engineering can emulate enzymatic proton channels, enabling precise control over hydride chemistry and guiding Mn-catalyzed CO<small><sub>2</sub></small> reduction exclusively toward formate formation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492555","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}
Sodium layered transition metal oxides (NaxTMO2), as the key cathode material for sodium-ion batteries, are still limited by the core issues such as irreversible phase transitions, air instability, and sluggish kinetics, generally leading to rapid performance degradation. The spinel-type (AB2O4) material, with its excellent structural stability and fast ion diffusion channels, provides an effective solution to overcome the challenges faced by NaxTMO2 through incorporation. In this study, we systematically review the construction methods of layered/spinel heterostructures and elucidate the core role of the spinel phase in optimizing the properties of NaxTMO2 cathodes. Subsequently, we discuss and integrate representative strategies for mitigating irreversible phase transitions, enhancing air stability, and accelerating Na+ transport kinetics, including multiphase composites, spinel sublayer coating and spinel coating strategies, etc. Finally, this review summarizes the challenges faced in spinel regulation strategies and provides corresponding research directions, while also looking forward to the development of layered/spinel heterostructures in various fields in the future. We believe that this analysis will inspire more theoretical understanding and practical guidance for the development of NaxTMO2 cathodes.
{"title":"Spinel integrated layered oxide cathodes for sodium-ion batteries: suppressing phase transitions, enhancing air stability, and accelerating Na+ transport","authors":"Rui Li, Yan-Jiang Li, Neng-Hua Xu, Bing-Bing Chen, Hai-Yan Hu, Yan-Fang Zhu, Yao Xiao","doi":"10.1039/d6sc00685j","DOIUrl":"https://doi.org/10.1039/d6sc00685j","url":null,"abstract":"Sodium layered transition metal oxides (Na<small><sub><em>x</em></sub></small>TMO<small><sub>2</sub></small>), as the key cathode material for sodium-ion batteries, are still limited by the core issues such as irreversible phase transitions, air instability, and sluggish kinetics, generally leading to rapid performance degradation. The spinel-type (AB<small><sub>2</sub></small>O<small><sub>4</sub></small>) material, with its excellent structural stability and fast ion diffusion channels, provides an effective solution to overcome the challenges faced by Na<small><sub><em>x</em></sub></small>TMO<small><sub>2</sub></small> through incorporation. In this study, we systematically review the construction methods of layered/spinel heterostructures and elucidate the core role of the spinel phase in optimizing the properties of Na<small><sub><em>x</em></sub></small>TMO<small><sub>2</sub></small> cathodes. Subsequently, we discuss and integrate representative strategies for mitigating irreversible phase transitions, enhancing air stability, and accelerating Na<small><sup>+</sup></small> transport kinetics, including multiphase composites, spinel sublayer coating and spinel coating strategies, <em>etc.</em> Finally, this review summarizes the challenges faced in spinel regulation strategies and provides corresponding research directions, while also looking forward to the development of layered/spinel heterostructures in various fields in the future. We believe that this analysis will inspire more theoretical understanding and practical guidance for the development of Na<small><sub><em>x</em></sub></small>TMO<small><sub>2</sub></small> cathodes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"31 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490097","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}
β-Lactams are versatile synthons for organic synthesis as well as valuable pharmacophores for drug development. Here, we describe a biocatalytic strategy for the enantioselective synthesis of allylic β-lactams via a hemoprotein-catalyzed intramolecular C(sp3)–H amidation reaction with dioxazolone substrates. Leveraging a stepwise radical mechanism and overriding the typical reactivity of metallonitrenes, this system provides access to a variety of β-lactam products with consistently high enantioselectivity (≥99% ee) by favoring the amination of an allylic C(sp3)-H bond over the more facile functionalization of the adjacent olefin group. This works expands the range of stereoselective strategies for C–N bond formation via C(sp3)–H functionalization and demonstrates the value of new-to-nature biocatalysis to promote chemical transformations not currently accessible through chemocatalysis.
{"title":"Highly stereoselective synthesis of allylic β-lactams via enzymatic C(sp3)–H amidation","authors":"Nawal Zahra Jafari, Zheyuan Wang, Anwita Chattopadhyay, Satyajit Roy, Rudi Fasan","doi":"10.1039/d6sc01440b","DOIUrl":"https://doi.org/10.1039/d6sc01440b","url":null,"abstract":"β-Lactams are versatile synthons for organic synthesis as well as valuable pharmacophores for drug development. Here, we describe a biocatalytic strategy for the enantioselective synthesis of allylic β-lactams <em>via</em> a hemoprotein-catalyzed intramolecular C(sp<small><sup>3</sup></small>)–H amidation reaction with dioxazolone substrates. Leveraging a stepwise radical mechanism and overriding the typical reactivity of metallonitrenes, this system provides access to a variety of β-lactam products with consistently high enantioselectivity (≥99% ee) by favoring the amination of an allylic C(sp<small><sup>3</sup></small>)-H bond over the more facile functionalization of the adjacent olefin group. This works expands the range of stereoselective strategies for C–N bond formation <em>via</em> C(sp<small><sup>3</sup></small>)–H functionalization and demonstrates the value of new-to-nature biocatalysis to promote chemical transformations not currently accessible through chemocatalysis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"111 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478927","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}
Silicon (Si) is considered a promising next-generation anode due to its ultrahigh theoretical capacity, yet the severe volume changes during cycling that cause interfacial instability and rapid capacity fade remain a major challenge. Conventional fluoride-based interfacial engineering seeks to enhance performance by inducing a LiF-rich SEI, but often overfocuses on LiF content while neglecting the structural and multifunctional requirements of the interphase. Herein, we propose an in-situ fluorination strategy to construct a composite coating layer comprising crystalline Li2SiF6 and amorphous Li3AlF6 (denoted as LSAF) on porous silicon (p-Si). This design creates a physicochemical barrier that simultaneously offers high ionic conductivity, superior mechanical strength, and effective electrolyte isolation. The LSAF-1 anode exhibits outstanding cycling stability, retaining 1238.0 mAh g-1 after 400 cycles at 2 A g-1. Its advantages are more pronounced under high-temperature and high-rate conditions. Furthermore, it shows remarkable performance in full cells paired with LiFePO4. Mechanistic studies reveal that this coating not only suppresses the accumulation of P/F-containing by-products at the electrode interface but also alleviates volumetric strain by enhancing interfacial mechanical strength. This research provides novel insights for rational interface engineering of Si anodes, advancing the design and development of high-performance anode materials for lithium-ion batteries.
由于其超高的理论容量，硅（Si）被认为是有前途的下一代阳极，但循环过程中严重的体积变化导致界面不稳定和容量快速衰减仍然是一个主要挑战。传统的基于氟化物的界面工程试图通过诱导富liff的SEI来提高性能，但往往过度关注liff含量，而忽略了界面的结构和多功能要求。在此，我们提出了一种原位氟化策略，在多孔硅（p-Si）上构建由晶体Li2SiF6和非晶Li3AlF6（记为LSAF）组成的复合涂层。这种设计创造了一个物理化学屏障，同时提供高离子电导率，优越的机械强度和有效的电解质隔离。lsa1阳极表现出出色的循环稳定性，在2 A g-1下循环400次后保持1238.0 mAh g-1。它的优点在高温和高速率条件下更为明显。此外，它在与LiFePO4配对的全电池中表现出卓越的性能。机理研究表明，该涂层不仅抑制了P/ f副产物在电极界面的积累，而且通过提高界面机械强度减轻了体积应变。该研究为硅阳极的合理界面工程提供了新的见解，推动了高性能锂离子电池负极材料的设计和开发。
{"title":"Functional-Oriented Design of Gradient Composite Fluoride Interphase for Enhanced Silicon Anode Performance","authors":"Yu Jing, Zhixing Wang, Huajun Guo, Xinhai Li, Hui Duan, Wenjie Peng, Guochun Yan, Guangchao Li, Jiexi Wang","doi":"10.1039/d6sc01590e","DOIUrl":"https://doi.org/10.1039/d6sc01590e","url":null,"abstract":"Silicon (Si) is considered a promising next-generation anode due to its ultrahigh theoretical capacity, yet the severe volume changes during cycling that cause interfacial instability and rapid capacity fade remain a major challenge. Conventional fluoride-based interfacial engineering seeks to enhance performance by inducing a LiF-rich SEI, but often overfocuses on LiF content while neglecting the structural and multifunctional requirements of the interphase. Herein, we propose an in-situ fluorination strategy to construct a composite coating layer comprising crystalline Li<small><sub>2</sub></small>SiF<small><sub>6</sub></small> and amorphous Li<small><sub>3</sub></small>AlF<small><sub>6</sub></small> (denoted as LSAF) on porous silicon (p-Si). This design creates a physicochemical barrier that simultaneously offers high ionic conductivity, superior mechanical strength, and effective electrolyte isolation. The LSAF-1 anode exhibits outstanding cycling stability, retaining 1238.0 mAh g<small><sup>-1</sup></small> after 400 cycles at 2 A g<small><sup>-1</sup></small>. Its advantages are more pronounced under high-temperature and high-rate conditions. Furthermore, it shows remarkable performance in full cells paired with LiFePO<small><sub>4</sub></small>. Mechanistic studies reveal that this coating not only suppresses the accumulation of P/F-containing by-products at the electrode interface but also alleviates volumetric strain by enhancing interfacial mechanical strength. This research provides novel insights for rational interface engineering of Si anodes, advancing the design and development of high-performance anode materials for lithium-ion batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"111 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147479014","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}
Qilong Zhang, Xu Zhou, Xiaofeng Shan, Fa He, Yuwei Bao, Hong Xu, Chun Zhu, Bixue Zhu
Ensuring the security and reliability of information has increasingly become a key issue for modern society, placing greater demands on encryption technologies and anti-counterfeiting materials. Therefore, the development of intelligent responsive materials with multi-mode encryption and protection capabilities has become crucial. In this study, an aldehyde–amine exchange approach was applied based on the traditional ESIPT–ISO (Excited state intramolecular proton transfer and cis to trans isomerization) color-switching mechanism of salicylaldehyde-aniline Schiff bases. The reaction between tetraphenylethyl salicylaldehyde and aniline derivatives generated eight Schiff base compounds. Five of these compounds displayed UV-triggered color change in the solid phase, whereas the other three exhibited fluorescence emission in solid form. Spectroscopic analysis, theoretical computation, and crystal-structure characterization clarified the mechanisms responsible for both color variation and stability. The stable compounds showed characteristic stacking configurations, and the hydroxyl groups formed weak interactions with nearby atoms, restricting the ESIPT transition and preventing color change under UV irradiation. This work presents the first systematic report on the effect of substituent variation on the ESIPT–ISO process, illustrating how weak interactions and packing modes can inhibit ESIPT. It also represents the first study describing substituent influences on the reverse ESIPT–ISO reaction. Finally, five UV-responsive color-switching materials were developed into color-shifting inks. Through pad and screen printing, these inks enabled encrypted information and anti-counterfeiting features on paper, inorganic, and fiber substrates, maintaining long-term stability for up to three years. Moreover, by utilizing differences in fading times among the photochromic molecules, color-changing inks were overprinted in specific sequences. Upon UV activation, this approach allowed multi-level time-space encryption and anti-counterfeiting of data.
{"title":"Switching between photochromism and photoluminescence in Schiff base derivatives by molecular design of end groups","authors":"Qilong Zhang, Xu Zhou, Xiaofeng Shan, Fa He, Yuwei Bao, Hong Xu, Chun Zhu, Bixue Zhu","doi":"10.1039/d6sc00735j","DOIUrl":"https://doi.org/10.1039/d6sc00735j","url":null,"abstract":"Ensuring the security and reliability of information has increasingly become a key issue for modern society, placing greater demands on encryption technologies and anti-counterfeiting materials. Therefore, the development of intelligent responsive materials with multi-mode encryption and protection capabilities has become crucial. In this study, an aldehyde–amine exchange approach was applied based on the traditional ESIPT–ISO (Excited state intramolecular proton transfer and <em>cis</em> to <em>trans</em> isomerization) color-switching mechanism of salicylaldehyde-aniline Schiff bases. The reaction between tetraphenylethyl salicylaldehyde and aniline derivatives generated eight Schiff base compounds. Five of these compounds displayed UV-triggered color change in the solid phase, whereas the other three exhibited fluorescence emission in solid form. Spectroscopic analysis, theoretical computation, and crystal-structure characterization clarified the mechanisms responsible for both color variation and stability. The stable compounds showed characteristic stacking configurations, and the hydroxyl groups formed weak interactions with nearby atoms, restricting the ESIPT transition and preventing color change under UV irradiation. This work presents the first systematic report on the effect of substituent variation on the ESIPT–ISO process, illustrating how weak interactions and packing modes can inhibit ESIPT. It also represents the first study describing substituent influences on the reverse ESIPT–ISO reaction. Finally, five UV-responsive color-switching materials were developed into color-shifting inks. Through pad and screen printing, these inks enabled encrypted information and anti-counterfeiting features on paper, inorganic, and fiber substrates, maintaining long-term stability for up to three years. Moreover, by utilizing differences in fading times among the photochromic molecules, color-changing inks were overprinted in specific sequences. Upon UV activation, this approach allowed multi-level time-space encryption and anti-counterfeiting of data.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478929","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}
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