Zhenghai Yang, Galiya R. Galimova, Chao He, Shane J. Goettl, Xiaohu Li, Alexander M. Mebel, Ralf I. Kaiser
The synthetic pathways to aromatic molecules inside photon-shielded dense molecular clouds remain a fundamental, unsolved enigma in astrochemistry and astrophysics, with low-temperature molecular growth routes involving aromatic radicals, such as prototype bicyclic naphthyl (C10H7•), implicated as key sources. Here, exploiting crossed molecular beam experiments augmented by electronic structure calculations, unexpected pathways are exposed leading to the gas-phase formation of 1- and 2-naphthyl via barrierless bimolecular reactions of atomic carbon (C) with indene (C9H8) and of dicarbon (C2) with styrene (C8H8) accompanied by ring expansion and cyclization together with aromatization. These facile routes challenge conventional wisdom that aromatic radicals are formed in deep space solely via “bright” gas-phase photochemistry of their closed-shell polycyclic aromatic hydrocarbon (PAH) precursors. A hitherto disregarded “dark” aromatic radical chemistry with aromatic radicals synthesized via gas-phase reactions offers new concepts on the chemical evolution of the chemistry of dark molecular clouds eventually culminating in the rapid formation of aromatics, fullerenes, and carbonaceous nanostructures.
{"title":"An Unconventional Dark Radical Chemistry in Dense Molecular Clouds: Directed Gas-Phase Formation of Naphthyl Radicals","authors":"Zhenghai Yang, Galiya R. Galimova, Chao He, Shane J. Goettl, Xiaohu Li, Alexander M. Mebel, Ralf I. Kaiser","doi":"10.1021/jacs.5c15459","DOIUrl":"https://doi.org/10.1021/jacs.5c15459","url":null,"abstract":"The synthetic pathways to aromatic molecules inside photon-shielded dense molecular clouds remain a fundamental, unsolved enigma in astrochemistry and astrophysics, with low-temperature molecular growth routes involving aromatic radicals, such as prototype bicyclic naphthyl (C<sub>10</sub>H<sub>7</sub><sup>•</sup>), implicated as key sources. Here, exploiting crossed molecular beam experiments augmented by electronic structure calculations, unexpected pathways are exposed leading to the gas-phase formation of 1- and 2-naphthyl via barrierless bimolecular reactions of atomic carbon (C) with indene (C<sub>9</sub>H<sub>8</sub>) and of dicarbon (C<sub>2</sub>) with styrene (C<sub>8</sub>H<sub>8</sub>) accompanied by ring expansion and cyclization together with aromatization. These facile routes challenge conventional wisdom that aromatic radicals are formed in deep space solely via “bright” gas-phase photochemistry of their closed-shell polycyclic aromatic hydrocarbon (PAH) precursors. A hitherto disregarded “dark” aromatic radical chemistry with aromatic radicals synthesized via gas-phase reactions offers new concepts on the chemical evolution of the chemistry of dark molecular clouds eventually culminating in the rapid formation of aromatics, fullerenes, and carbonaceous nanostructures.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"34 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732599","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}
Kai Xiong, Cheng Ouyang, Fa Wang, Ya Wen, Xianbo Wu, Jinzhe Liang, Yu Chen, Chung-Hang Leung, Hui Chao
G-quadruplex (G4) DNA is a critical target for disease monitoring. However, while existing probes primarily focus on nuclear G4s, their mitochondrial counterparts (mitoG4) remain underexplored. The few available mitoG4 probes are limited by the shallow penetration depth of one-photon excitation and generally permit only qualitative detection. To address these challenges, we developed a mitochondria-localized iridium(III) complex, Ir2PDP. By screening a library of seventy-five distinct mitoG4 sequences, we validated its specificity, which results in up to a 113.4-fold emission enhancement and a 740 ns lifetime extension, all without perturbing native mitoG4 dynamics. Owing to its large two-photon absorption cross-section and exceptional antiphotobleaching capability, Ir2PDP enables two-photon phosphorescence lifetime imaging (PLIM) that differentiates eight specific mitoG4 structures and quantifies their abundance in live cells and zebrafish. To the best of our knowledge, Ir2PDP represents the first two-photon PLIM probe capable of quantitative mitoG4 DNA detection.
{"title":"Facilitating Quantitation of Mitochondrial G-Quadruplex DNA with an Iridium(III) Two-Photon Phosphorescence Lifetime Imaging Probe","authors":"Kai Xiong, Cheng Ouyang, Fa Wang, Ya Wen, Xianbo Wu, Jinzhe Liang, Yu Chen, Chung-Hang Leung, Hui Chao","doi":"10.1021/jacs.5c17409","DOIUrl":"https://doi.org/10.1021/jacs.5c17409","url":null,"abstract":"G-quadruplex (G4) DNA is a critical target for disease monitoring. However, while existing probes primarily focus on nuclear G4s, their mitochondrial counterparts (mitoG4) remain underexplored. The few available mitoG4 probes are limited by the shallow penetration depth of one-photon excitation and generally permit only qualitative detection. To address these challenges, we developed a mitochondria-localized iridium(III) complex, <b>Ir</b><b><sub>2</sub></b><b>PDP</b>. By screening a library of seventy-five distinct mitoG4 sequences, we validated its specificity, which results in up to a 113.4-fold emission enhancement and a 740 ns lifetime extension, all without perturbing native mitoG4 dynamics. Owing to its large two-photon absorption cross-section and exceptional antiphotobleaching capability, <b>Ir</b><b><sub>2</sub></b><b>PDP</b> enables two-photon phosphorescence lifetime imaging (PLIM) that differentiates eight specific mitoG4 structures and quantifies their abundance in live cells and zebrafish. To the best of our knowledge, <b>Ir</b><b><sub>2</sub></b><b>PDP</b> represents the first two-photon PLIM probe capable of quantitative mitoG4 DNA detection.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"66 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732155","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}
Run-Hang Chen, Jian-Hua Long, Zi-Jian Chen, Xian Zeng, Yan-Fei Chen, Shi-Rui Zhao, Qing-Qing Yuan, Wei-Fan Chen, Lin Liu, Jizhuang Wang, Yin Ning, De-Shan Bin, Dan Li
K-ion batteries (KIBs) with abundant resources are being extensively pursued, but high-capacity anode materials for storing the larger-sized K ions suffer from electrochemical instability. This instability worsens at elevated temperatures, as increasing the temperature would exacerbate the chemical and mechanical instability of the electrode and its interface with the electrolytes, making the pursuit of stable high-capacity anode materials for high-temperature KIBs a formidable challenge. Herein, we demonstrated that low-crystallinity zinc sulfide (ZnS) embedded in a three-dimensional macroporous carbon skeleton (3D-M-ZnS) could act as a high-performance anode for room- and high-temperature KIBs. The well-dispersed low-crystallinity ZnS can deliver superior electrochemical activity; the 3D macroporous architecture with hollow building blocks can facilitate the K+ transport and alleviate volume deformation, thus achieving high capacity (400 mAh g–1) and ultrastable cyclability with ∼100% retention of initial capacity for 5600 cycles at room temperature (RT). Even at an extreme temperature of 60 °C, this 3D-M-ZnS composite still promised an outstanding cyclability (no capacity fading over 430 cycles at 2A g–1) with a high reversible capacity (447 mAh g–1 at 30 mA g–1) and a superior rate, which is a much better comprehensive battery performance than that of the existing high-temperature KIBs anodes. This contribution opened an effective avenue in building reliable anodes for high-performance K-ion storage, even under extreme temperatures.
资源丰富的K离子电池正受到广泛的关注，但用于存储大容量K离子的高容量负极材料存在电化学不稳定性问题。这种不稳定性在高温下会恶化，因为温度升高会加剧电极及其与电解质界面的化学和机械不稳定性，因此为高温kib寻求稳定的高容量阳极材料是一项艰巨的挑战。在这里，我们证明了嵌入在三维大孔碳骨架（3D-M-ZnS）中的低结晶度硫化锌（ZnS）可以作为室温和高温kib的高性能阳极。分散良好的低结晶度ZnS具有优异的电化学活性；具有中空构件的3D大孔结构可以促进K+的运输并减轻体积变形，从而实现高容量（400 mAh g-1）和超稳定的可循环性，在室温（RT）下5600次循环的初始容量保持约100%。即使在60°C的极端温度下，这种3D-M-ZnS复合材料仍然具有出色的可循环性（在2A g-1下430次循环时容量不会衰减），具有高可逆容量（在30 mA g-1下447 mAh g-1）和优越的倍率，比现有的高温KIBs阳极具有更好的综合电池性能。这一贡献为构建高性能k离子存储的可靠阳极开辟了一条有效途径，即使在极端温度下也是如此。
{"title":"3D Macroporous Engineering of Metal Sulfide-Based Materials for High-Capacity and Ultrastable Potassium Storage under Room and Extreme Temperatures","authors":"Run-Hang Chen, Jian-Hua Long, Zi-Jian Chen, Xian Zeng, Yan-Fei Chen, Shi-Rui Zhao, Qing-Qing Yuan, Wei-Fan Chen, Lin Liu, Jizhuang Wang, Yin Ning, De-Shan Bin, Dan Li","doi":"10.1021/jacs.5c12045","DOIUrl":"https://doi.org/10.1021/jacs.5c12045","url":null,"abstract":"K-ion batteries (KIBs) with abundant resources are being extensively pursued, but high-capacity anode materials for storing the larger-sized K ions suffer from electrochemical instability. This instability worsens at elevated temperatures, as increasing the temperature would exacerbate the chemical and mechanical instability of the electrode and its interface with the electrolytes, making the pursuit of stable high-capacity anode materials for high-temperature KIBs a formidable challenge. Herein, we demonstrated that low-crystallinity zinc sulfide (ZnS) embedded in a three-dimensional macroporous carbon skeleton (3D-M-ZnS) could act as a high-performance anode for room- and high-temperature KIBs. The well-dispersed low-crystallinity ZnS can deliver superior electrochemical activity; the 3D macroporous architecture with hollow building blocks can facilitate the K<sup>+</sup> transport and alleviate volume deformation, thus achieving high capacity (400 mAh g<sup>–1</sup>) and ultrastable cyclability with ∼100% retention of initial capacity for 5600 cycles at room temperature (RT). Even at an extreme temperature of 60 °C, this 3D-M-ZnS composite still promised an outstanding cyclability (no capacity fading over 430 cycles at 2A g<sup>–1</sup>) with a high reversible capacity (447 mAh g<sup>–1</sup> at 30 mA g<sup>–1</sup>) and a superior rate, which is a much better comprehensive battery performance than that of the existing high-temperature KIBs anodes. This contribution opened an effective avenue in building reliable anodes for high-performance K-ion storage, even under extreme temperatures.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732557","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}
Brianna Check, Ji Yong Choi, Joe Santarelli, Chenwei Lu, Hoai T. B. Pham, Gavin Lopez, Casey M. Davis, Jihye Park
Metal–organic frameworks (MOFs) can exhibit tunable electrochromic properties through redox-active metal nodes or linkers, yet their inherently poor electrical conductivity confines redox activity and requires high operating voltages (>1 V), limiting device integration. Electrically conductive MOFs (c-MOFs) can overcome this but often rely on specific metal–linker combinations, due to the limited redox-active organic functional groups available in c-MOFs. Here, we leverage Cu-truxone, a c-MOF featuring redox-active carbonyl (C═O) groups with a conductivity of 1.9 × 10–2 S cm–1 that realizes linker-centric electrochromism. We developed an in situ growth method in which Cu-truxone is directly synthesized on a mercaptobenzoic acid-functionalized fluorine-doped tin oxide (FTO) substrate. This enables pronounced and efficient electrochromic switching at a low voltage range (<1.0 V) with a high coloration efficiency of 193.6 cm2 C–1. Our findings showcase the potential of c-MOFs with redox-active functional groups in linkers for electrochromic applications.
{"title":"Harnessing Truxone-Based Electrically Conductive Metal–Organic Framework for Electrochromism","authors":"Brianna Check, Ji Yong Choi, Joe Santarelli, Chenwei Lu, Hoai T. B. Pham, Gavin Lopez, Casey M. Davis, Jihye Park","doi":"10.1021/jacs.5c17399","DOIUrl":"https://doi.org/10.1021/jacs.5c17399","url":null,"abstract":"Metal–organic frameworks (MOFs) can exhibit tunable electrochromic properties through redox-active metal nodes or linkers, yet their inherently poor electrical conductivity confines redox activity and requires high operating voltages (>1 V), limiting device integration. Electrically conductive MOFs (c-MOFs) can overcome this but often rely on specific metal–linker combinations, due to the limited redox-active organic functional groups available in c-MOFs. Here, we leverage Cu-truxone, a c-MOF featuring redox-active carbonyl (C═O) groups with a conductivity of 1.9 × 10<sup>–2</sup> S cm<sup>–1</sup> that realizes linker-centric electrochromism. We developed an <i>in situ</i> growth method in which Cu-truxone is directly synthesized on a mercaptobenzoic acid-functionalized fluorine-doped tin oxide (FTO) substrate. This enables pronounced and efficient electrochromic switching at a low voltage range (<1.0 V) with a high coloration efficiency of 193.6 cm<sup>2</sup> C<sup>–1</sup>. Our findings showcase the potential of c-MOFs with redox-active functional groups in linkers for electrochromic applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"34 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732154","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}
CALF-20 is a metal–organic framework (MOF) that is known for its exceptional CO2 selectivity under humid conditions. However, the molecular mechanism underlying its humidity-induced structural phase transitions and how water and CO2 compete at the molecular level remain unclear. In this work, we developed a machine learning potential (MLP) with first-principles accuracy to investigate how water dynamics drive the transition from the open-pore (OP) to the closed-pore (CP) phase. We identify that water coordination at the Zn node forms hydrogen-bonded water dimers and trimers along the [011] diffusion channel, which are critical for the OP-CP phase transition. In the CP structure, these Zn-bound water networks exhibit residence times exceeding hundreds of picoseconds and occupy approximately half of the Zn nodes, reproducing previous experiments for the first time. Remarkably, preadsorbed CO2 disrupts this water network. This effect is further supported by diffuse reflectance infrared Fourier transform spectroscopy, which reveals suppressed O–H stretching signals in CO2 preloaded samples, indicating the inhibition of hydrogen-bonded water cluster formation. These findings provide a mechanistic explanation for the experimentally observed delay in the water uptake under competitive CO2/H2O adsorptions. Moreover, our MLP simulations accurately reproduce the water adsorption isotherm and experimental X-ray diffraction patterns of the α, β, τ, and γ phases, establishing a direct link between the microscopic structure and the macroscopic phase behavior observed in experiments. This study provides molecular-level insights into humidity-induced transitions in flexible MOFs and demonstrates a simulation framework for modeling guest-responsive behavior in soft porous materials.
{"title":"Unraveling the Humidity-Induced Phase Transition in CALF-20 via Machine Learning Potentials","authors":"Poobodin Mano, Klichchupong Dabsamut, Ching-Ming Wei, Siriporn Kosawatthanakun, Bunyarat Rungtaweevoranit, Supawadee Namuangruk, Kaito Takahashi","doi":"10.1021/jacs.5c18944","DOIUrl":"https://doi.org/10.1021/jacs.5c18944","url":null,"abstract":"CALF-20 is a metal–organic framework (MOF) that is known for its exceptional CO<sub>2</sub> selectivity under humid conditions. However, the molecular mechanism underlying its humidity-induced structural phase transitions and how water and CO<sub>2</sub> compete at the molecular level remain unclear. In this work, we developed a machine learning potential (MLP) with first-principles accuracy to investigate how water dynamics drive the transition from the open-pore (OP) to the closed-pore (CP) phase. We identify that water coordination at the Zn node forms hydrogen-bonded water dimers and trimers along the [011] diffusion channel, which are critical for the OP-CP phase transition. In the CP structure, these Zn-bound water networks exhibit residence times exceeding hundreds of picoseconds and occupy approximately half of the Zn nodes, reproducing previous experiments for the first time. Remarkably, preadsorbed CO<sub>2</sub> disrupts this water network. This effect is further supported by diffuse reflectance infrared Fourier transform spectroscopy, which reveals suppressed O–H stretching signals in CO<sub>2</sub> preloaded samples, indicating the inhibition of hydrogen-bonded water cluster formation. These findings provide a mechanistic explanation for the experimentally observed delay in the water uptake under competitive CO<sub>2</sub>/H<sub>2</sub>O adsorptions. Moreover, our MLP simulations accurately reproduce the water adsorption isotherm and experimental X-ray diffraction patterns of the α, β, τ, and γ phases, establishing a direct link between the microscopic structure and the macroscopic phase behavior observed in experiments. This study provides molecular-level insights into humidity-induced transitions in flexible MOFs and demonstrates a simulation framework for modeling guest-responsive behavior in soft porous materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732156","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}
Soichiro Seki, Lorenzo Cupellini, David Bína, Elena Betti, Petra Urajová, Hideaki Tanaka, Tomoko Miyata, Keiichi Namba, Genji Kurisu, Tomáš Polívka, Radek Litvín, Ritsuko Fujii
Photosynthetic organisms employ light-harvesting complexes (LHCs) to optimize energy capture under variable light conditions. The freshwater eustigmatophyte Trachydiscus minutus accumulates a red-shifted violaxanthin–chlorophyll protein (rVCP) that contributes to far-red light harvesting using only chlorophyll (Chl) a molecules, without chemical modification or substitution of pigments. Based on high-resolution cryo-EM and multiscale quantum chemical calculations, we uncovered a heterodimer-based tetrameric architecture, representing a unique oligomerization mode among LHCs. Within each heterodimer, Chls a are distinctively arranged adjacent to the terminal emitter, forming an unprecedentedly extended chlorophyll cluster. Quantum chemical calculations reveal three strong exciton-coupled pigment domains, two of which reside in the large cluster and solely account for the intense far-red absorption near 700 nm without contributions from charge–transfer states. Our structural and quantum chemical characterizations of far-red light harvesting reveal a molecular mechanism of red spectral tuning that relies on protein-controlled excitonic coupling of identical Chl a pigments, as demonstrated here in this eustigmatophyte, highlighting diverse adaptations for harvesting spectrally shifted, low-energy light.
{"title":"Exciton Delocalization Promotes Far-Red Absorption in a Tetrameric Chlorophyll a Light-Harvesting Complex from Trachydiscus minutus","authors":"Soichiro Seki, Lorenzo Cupellini, David Bína, Elena Betti, Petra Urajová, Hideaki Tanaka, Tomoko Miyata, Keiichi Namba, Genji Kurisu, Tomáš Polívka, Radek Litvín, Ritsuko Fujii","doi":"10.1021/jacs.5c17299","DOIUrl":"https://doi.org/10.1021/jacs.5c17299","url":null,"abstract":"Photosynthetic organisms employ light-harvesting complexes (LHCs) to optimize energy capture under variable light conditions. The freshwater eustigmatophyte <i>Trachydiscus minutus</i> accumulates a red-shifted violaxanthin–chlorophyll protein (rVCP) that contributes to far-red light harvesting using only chlorophyll (Chl) <i>a</i> molecules, without chemical modification or substitution of pigments. Based on high-resolution cryo-EM and multiscale quantum chemical calculations, we uncovered a heterodimer-based tetrameric architecture, representing a unique oligomerization mode among LHCs. Within each heterodimer, Chls <i>a</i> are distinctively arranged adjacent to the terminal emitter, forming an unprecedentedly extended chlorophyll cluster. Quantum chemical calculations reveal three strong exciton-coupled pigment domains, two of which reside in the large cluster and solely account for the intense far-red absorption near 700 nm without contributions from charge–transfer states. Our structural and quantum chemical characterizations of far-red light harvesting reveal a molecular mechanism of red spectral tuning that relies on protein-controlled excitonic coupling of identical Chl <i>a</i> pigments, as demonstrated here in this eustigmatophyte, highlighting diverse adaptations for harvesting spectrally shifted, low-energy light.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"39 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732153","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}
Catalytic conversion of acid waste gases into value-added chemicals is crucial for sustainable carbon and sulfur utilization, and designing efficient and stable catalysts shows great significance in achieving this goal. Herein, we report an olefin-linked, bipyridine-functionalized COF with atomically dispersed Cu active sites (xCu@COF-PzBpy) that combines high specific surface area, robust stability, and an asymmetric Cu–N4 coordination geometry induced by the interlayer stress effect. The newly engineered Cu–N4 active centers demonstrate enhanced activation capability for both acid gases and epoxides, endowing xCu@COF-PzBpy with an exceptional catalytic performance for their upcycling under ambient conditions. This performance outperforms nearly all previously reported catalysts. Similarly, the high catalytic activities of xCu@COF-PzBpy can be extended to the COS and SO2 cycloaddition. No activity loss, Cu leaching, and/or aggregation were observed over 10 cycles. This work provides a new strategy for developing efficient and reusable catalysts for acid waste gas upcycling, addressing environmental challenges while enabling green and sustainable cycles.
{"title":"Upcycling of Acid Waste Gases Using Asymmetric Atomic-Copper-Anchored Covalent Organic Framework Catalyst","authors":"Liping Zheng, Fengqing Liu, Yabin Zhou, Shouchao Zhong, Yongfang Qu, Yong Zheng, Anmin Zheng, He Cheng, Fujian Liu, Lilong Jiang","doi":"10.1021/jacs.5c13792","DOIUrl":"https://doi.org/10.1021/jacs.5c13792","url":null,"abstract":"Catalytic conversion of acid waste gases into value-added chemicals is crucial for sustainable carbon and sulfur utilization, and designing efficient and stable catalysts shows great significance in achieving this goal. Herein, we report an olefin-linked, bipyridine-functionalized COF with atomically dispersed Cu active sites (xCu@COF-PzBpy) that combines high specific surface area, robust stability, and an asymmetric Cu–N<sub>4</sub> coordination geometry induced by the interlayer stress effect. The newly engineered Cu–N<sub>4</sub> active centers demonstrate enhanced activation capability for both acid gases and epoxides, endowing xCu@COF-PzBpy with an exceptional catalytic performance for their upcycling under ambient conditions. This performance outperforms nearly all previously reported catalysts. Similarly, the high catalytic activities of xCu@COF-PzBpy can be extended to the COS and SO<sub>2</sub> cycloaddition. No activity loss, Cu leaching, and/or aggregation were observed over 10 cycles. This work provides a new strategy for developing efficient and reusable catalysts for acid waste gas upcycling, addressing environmental challenges while enabling green and sustainable cycles.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"148 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145732157","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}
Ji Hoon Kim, Ji Seon Kim, Yong Hui Kim, Byeongsun Jun, Yong Jun Jang, Sang Uck Lee
Significant attention has been devoted to developing novel solid-state electrolytes (SSEs) with high ionic conductivity for all-solid-state batteries (ASSBs). However, most studies have primarily focused on compositional substitutions, often overlooking the fundamental role of inherent crystal structures on ion transport. To address this, we introduce a theoretical crystal structure prediction (CSP) approach based on the machine-learning moment tensor potential (MTP). The proposed approach successfully identifies novel SSE structures and reproduces 12 experimental crystal structures. Using a phase-diagram-guided strategy, CSP is applied to four promising SSE candidates, Li2SiS3, Li2GeS3, Li4SiGeS6, and Li4SiSnS6, to assess their polyhedral connectivity, relative stability, and Li-ion transport properties. The results reveal that metastable edge-sharing phases exhibit superior Li-ion mobility compared with their stable corner-sharing counterparts. This superior conductivity is attributed to the Li-ion accessible volume, quantified by the packing ratio (fraction of the unit cell volume occupied by nonconductive volume) and by the dynamic distortion of the Li–S4 sublattice, which represents the local environment encountered by migrating Li-ions. The metastable phases feature higher packing efficiency, larger Li–S4 sublattice volume, and greater distortion, all of which contribute to improved Li-ion transport. This study highlights the potential of CSP to design novel SSEs and high-performance ASSBs.
{"title":"Machine Learning-Assisted Crystal Structure Prediction of Solid-State Electrolytes Reveals Superior Ionic Conductivity in Metastable Edge-Sharing Phases","authors":"Ji Hoon Kim, Ji Seon Kim, Yong Hui Kim, Byeongsun Jun, Yong Jun Jang, Sang Uck Lee","doi":"10.1021/jacs.5c15665","DOIUrl":"https://doi.org/10.1021/jacs.5c15665","url":null,"abstract":"Significant attention has been devoted to developing novel solid-state electrolytes (SSEs) with high ionic conductivity for all-solid-state batteries (ASSBs). However, most studies have primarily focused on compositional substitutions, often overlooking the fundamental role of inherent crystal structures on ion transport. To address this, we introduce a theoretical crystal structure prediction (CSP) approach based on the machine-learning moment tensor potential (MTP). The proposed approach successfully identifies novel SSE structures and reproduces 12 experimental crystal structures. Using a phase-diagram-guided strategy, CSP is applied to four promising SSE candidates, Li<sub>2</sub>SiS<sub>3</sub>, Li<sub>2</sub>GeS<sub>3</sub>, Li<sub>4</sub>SiGeS<sub>6</sub>, and Li<sub>4</sub>SiSnS<sub>6</sub>, to assess their polyhedral connectivity, relative stability, and Li-ion transport properties. The results reveal that metastable edge-sharing phases exhibit superior Li-ion mobility compared with their stable corner-sharing counterparts. This superior conductivity is attributed to the Li-ion accessible volume, quantified by the packing ratio (fraction of the unit cell volume occupied by nonconductive volume) and by the dynamic distortion of the Li–S<sub>4</sub> sublattice, which represents the local environment encountered by migrating Li-ions. The metastable phases feature higher packing efficiency, larger Li–S<sub>4</sub> sublattice volume, and greater distortion, all of which contribute to improved Li-ion transport. This study highlights the potential of CSP to design novel SSEs and high-performance ASSBs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"2 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729146","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}
Zhi-Hao Chen, Feng Chen, Olafs Daugulis, Maurice Brookhart
A single-step route to heterotelechelic polyethylene is enabled by palladium-diimine-catalyzed polymerization of ethylene using vinylsilanes as chain-transfer agents. The reaction affords α-alkenyl-ω-silyl end-capped heterotelechelic polymers whose molecular weights are controllable over a wide range by adjusting the [ethylene]/[vinylsilane] molar ratios. Notably, highly efficient end-capping with silanes carrying a variety of functionalities can be achieved under the optimized conditions. The alkenyl- and silyl-terminated telechelics serve as polymer precursors for further reactions and can be converted into additional telechelic functionalized polyolefins in good yields.
{"title":"Vinylsilanes as Chain-Transfer Agents in Ethylene Polymerization: Direct Synthesis of Heterotelechelic Polyolefins","authors":"Zhi-Hao Chen, Feng Chen, Olafs Daugulis, Maurice Brookhart","doi":"10.1021/jacs.5c15808","DOIUrl":"https://doi.org/10.1021/jacs.5c15808","url":null,"abstract":"A single-step route to heterotelechelic polyethylene is enabled by palladium-diimine-catalyzed polymerization of ethylene using vinylsilanes as chain-transfer agents. The reaction affords α-alkenyl-ω-silyl end-capped heterotelechelic polymers whose molecular weights are controllable over a wide range by adjusting the [ethylene]/[vinylsilane] molar ratios. Notably, highly efficient end-capping with silanes carrying a variety of functionalities can be achieved under the optimized conditions. The alkenyl- and silyl-terminated telechelics serve as polymer precursors for further reactions and can be converted into additional telechelic functionalized polyolefins in good yields.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"143 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729252","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}
Covalent organic framework (COF) membranes hold immense potential for aqueous separations, yet their inherently large pore apertures and insufficient film crystallinity often limit their performance, particularly in challenging applications like water desalination. Here, we address these limitations by introducing an acid-modulated interfacial synthesis (AMIS) strategy to precisely engineer an ultramicroporous, highly crystalline Turing COF membrane. A detailed mechanistic investigation reveals that acetic acid forms hydrogen-bonded adducts with the hydrophilic aliphatic linker, oxalyl dihydrazide (ODH), finely tuning both its reactivity and diffusivity during Schiff base condensation with the linker, 1,3,5-triformylphloroglucinol (Tp). This modulated reaction–diffusion behavior not only facilitates the formation of a unique stripe-patterned Turing architecture but also enables sufficient defect self-correction via reaction retardation, yielding a COF film with high crystallinity. The resultant aliphatic ODH–COF membranes exhibit a unique ABC stacking mode and a sub-6-Å pore aperture, validated by experimental data and simulations. These characteristics, working in concert, enable the ODH–COF membranes to achieve record-high NaCl rejection of 99.7% with a water permeance of 0.82 L m–2 h–1 bar–1, surpassing previously reported state-of-the-art COF membranes in pressure-driven separation processes. Coupled with robust fouling resistance and long-term stability, this work substantially advances COF membrane technology for sustainable and efficient water management.
共价有机框架（COF）膜在水分离方面具有巨大的潜力，但其固有的大孔径和膜结晶度不足往往限制了其性能，特别是在具有挑战性的应用中，如海水淡化。在这里，我们通过引入酸调制界面合成（AMIS）策略来解决这些限制，以精确地设计超微孔，高结晶的图灵COF膜。详细的机理研究表明，乙酸与亲水性脂肪连接剂草酰二肼（ODH）形成氢键加合物，并在与连接剂1,3,5-三甲酰间苯三酚（Tp）的席夫碱缩合过程中精细调节了其反应性和扩散性。这种调制的反应扩散行为不仅有助于形成独特的条纹图灵结构，而且还可以通过反应延迟进行足够的缺陷自校正，从而产生具有高结晶度的COF薄膜。所得的脂肪族ODH-COF膜具有独特的ABC堆叠模式和低于6-Å的孔径，实验数据和模拟验证了这一点。这些特性共同作用，使ODH-COF膜能够达到创纪录的99.7%的NaCl截除率，水渗透率为0.82 L m-2 h-1 bar-1，在压力驱动分离过程中超过了先前报道的最先进的COF膜。再加上强大的抗污染性和长期稳定性，这项工作大大推进了COF膜技术的可持续和高效水管理。
{"title":"Precision-Engineered Crystalline Covalent Organic Framework Membranes with Staggered ABC Stacking for High-Performance Desalination","authors":"Jingsi Yuan, Zhaohuan Mai, Makenna Parkinson, Yunqiu Zhou, Jingwei Hou, Xueli Cao, Shi-Peng Sun, Yatao Zhang, Junyong Zhu, Menachem Elimelech","doi":"10.1021/jacs.5c16195","DOIUrl":"https://doi.org/10.1021/jacs.5c16195","url":null,"abstract":"Covalent organic framework (COF) membranes hold immense potential for aqueous separations, yet their inherently large pore apertures and insufficient film crystallinity often limit their performance, particularly in challenging applications like water desalination. Here, we address these limitations by introducing an acid-modulated interfacial synthesis (AMIS) strategy to precisely engineer an ultramicroporous, highly crystalline Turing COF membrane. A detailed mechanistic investigation reveals that acetic acid forms hydrogen-bonded adducts with the hydrophilic aliphatic linker, oxalyl dihydrazide (ODH), finely tuning both its reactivity and diffusivity during Schiff base condensation with the linker, 1,3,5-triformylphloroglucinol (Tp). This modulated reaction–diffusion behavior not only facilitates the formation of a unique stripe-patterned Turing architecture but also enables sufficient defect self-correction via reaction retardation, yielding a COF film with high crystallinity. The resultant aliphatic ODH–COF membranes exhibit a unique ABC stacking mode and a sub-6-Å pore aperture, validated by experimental data and simulations. These characteristics, working in concert, enable the ODH–COF membranes to achieve record-high NaCl rejection of 99.7% with a water permeance of 0.82 L m<sup>–2</sup> h<sup>–1</sup> bar<sup>–1</sup>, surpassing previously reported state-of-the-art COF membranes in pressure-driven separation processes. Coupled with robust fouling resistance and long-term stability, this work substantially advances COF membrane technology for sustainable and efficient water management.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"366 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145729255","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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