Journal of the American Chemical Society最新文献

{"title":"Chirality-Directed Molecular Weaving","authors":"Xuedong Xiao,Zhewen Guo,Sheng-Nan Lei,Wutong Du,Guangguo Wang,Mengbin Wang,Ding Xiao,Tianyu Shan,Jiao Wang,Liya Chen,Cheng Liu,Le Shi,Herman H. Y. Sung,Ian D. Williams,Jacky W. Y. Lam,Guangfeng Li,Ben Zhong Tang,Feihe Huang","doi":"10.1021/jacs.6c13196","DOIUrl":"https://doi.org/10.1021/jacs.6c13196","url":null,"abstract":"Weaving molecular strands in a manner akin to macroscale fabrics is considered a highly promising strategy for the development of novel polymeric materials. However, existing molecular weaving strategies rely on metal templates or solvent assistance for topological control, which limits molecular weaving to specific conditions. Here, we present a new molecular weaving strategy based on chirality-directed assembly. It can be used in the construction of two-dimensional molecularly woven polymers in various solvents and at different temperatures, all without the use of metal templates or solvent assistance. Furthermore, leveraging the characteristic undulating structure of the woven topology, this strategy provides a unique pathway for tuning the porous separation performance and mechanical properties of molecularly woven materials. These advancements will expedite molecular weaving technology with unprecedented properties.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"81 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210911","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":"ZnO-Enhanced Cu/ZrO2 for Photothermal Catalytic\u0000CO2 Hydrogenation to Methanol","authors":"Zhen Ren,Shuyi Li,Mingyu Chu,Haoyi Tang,Chengyu Li,Meng Wang,Ding Ma","doi":"10.1021/jacs.6c14346","DOIUrl":"https://doi.org/10.1021/jacs.6c14346","url":null,"abstract":"Abstract The photothermal conversion of CO2 to methanol represents a sustainable pathway for energy storage and carbon neutrality. However, most highly active photothermal catalysts have been evaluated under Xenon-lamp irradiation, in which the photothermal effect arises predominantly from the infrared region. This practice may therefore lead to an underutilization of the ultraviolet (UV) spectrum available in natural solar light. To address this limitation, we designed a composite catalyst by strategically incorporating the semiconductor ZnO into a Cu/ZrO2 system. This design enables complementary light absorption: Cu effectively harnesses visible/near-infrared light, while ZnO extends the response into the UV range. Comprehensive characterizations confirm that the introduction of Zn significantly enhances the light-harvesting capability without altering the Cu active sites. Consequently, the optimized Cu/ZrO2–ZnO catalyst exhibits a remarkable enhancement in photothermal reaction, particularly under UV light, while maintaining CO2 hydrogenation activity. When evaluated under concentrated real sunlight, the catalyst achieves a methanol production rate of 2.7 mmol g–1 h–1, attributable to its efficient full-spectrum utilization. This work not only provides an efficient catalyst for CO2 hydrogenation but also demonstrates a general strategy for maximizing solar energy conversion in photothermal catalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"292 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210413","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":"Layer Engineering of\u0000Quantum Organic–Inorganic\u0000Superlattices by Thermodynamic Design","authors":"Yang Liu,Ziren Wang,Xiaolin Tai,Xuzhe Song,Minghao Wang,Yuqiao Guo,Ying Yang,Yiwei Zhang,Zhengming Shang,Baidu Zhang,Guoliang Hu,Yi Liu,Zhe Sun,Haifeng Lv,Yue Lin,Xiaojun Wu,Yi Xie,Changzheng Wu","doi":"10.1021/jacs.6c11170","DOIUrl":"https://doi.org/10.1021/jacs.6c11170","url":null,"abstract":"Abstract Quantum organic–inorganic superlattices, constructed by vertically stacking two-dimensional inorganic crystals and organic molecular layers, offer a powerful platform for encoding emergent electronic states through an interfacial design. However, the precise layer engineering of such hybrid architectures, particularly the deterministic control over vertical stacking periodicities, has remained elusive because of the absence of a predictive thermodynamic framework governing the staging effect in hybrid systems. Here, we demonstrate that thermodynamic design, based on the quantitative competition between intercalant chemical potential and host elastic deformation energy, provides a principled route to programmable layer engineering of organic–inorganic superlattices. By precisely modulating the chemical potential of the intercalant, we achieve selective access to stage-1 intercalation (alternating 1-layer (1L) molecule/1L-SnSe2) and stage-2 intercalation (alternating 1L-molecule/2L-SnSe2) configurations with high structural fidelity. Atomic-resolution imaging reveals long-range periodic order across both staging phases, while angle-resolved photoemission spectroscopy reveals that the engineered layer sequence directly governs the interfacial charge transfer and electronic band structure evolution. The resulting superlattices exhibit stacking-dependent carrier densities and programmable superconducting transitions, establishing the layer sequence as a synthetic handle for quantum functionality. This work establishes thermodynamic design as a guiding principle for the rational layer engineering of quantum-hybrid solids.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"311 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210452","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":"Accelerated\u0000Zeolite Defect Healing Suppresses Oxygen-Containing\u0000Species Trapping for Tandem Propene Epoxidation","authors":"Dong Lin,Xin Zhou,Yang Xu,Richard J. Lewis,Zongzhuang Sun,Defu Yin,Yongxiang Wang,Zhenyi Liu,Jingyuan Shang,Zhe Ma,Qiang Wang,Feng Deng,Chaohe Yang,De Chen,Graham J. Hutchings,Xiang Feng","doi":"10.1021/jacs.6c17355","DOIUrl":"https://doi.org/10.1021/jacs.6c17355","url":null,"abstract":"Abstract Selective oxidation of chemical feedstocks with in situ-generated H2O2 offers a sustainable route to high-value oxygenates, yet such tandem catalysis is often fundamentally limited by the trapping of oxygen-containing species, including H2O2-derived intermediates and oxygenated products in zeolite microenvironments, where they undergo nonproductive decomposition and side reactions. Herein, we overcome this limitation by accelerating titanosilicalite hydroxyl defect healing through intensified nucleation and subsequent accelerated crystal growth. The resulting defect-healed microenvironment facilitates the transport of in situ-generated H2O2 between bifunctional active sites while suppressing its nonproductive decomposition to H2O. Moreover, it accelerates product propylene oxide (PO) desorption by weakening hydrogen bond interactions between PO and hydroxyl defects, thereby suppressing ring-opening and overoxidation side reactions. Consequently, the defect-healed Au/TS-1 catalyst exhibits a 1.8-fold enhancement in the PO formation rate and a 2.1-fold increase in Au-based productivity. This defect-healing strategy is broadly applicable to titanosilicates, aluminosilicates, and pure-silica zeolites and can be readily extended to a 10 L scale process, delivering reductions of 21% in production cost and 54% in carbon emissions compared with conventional TS-1 synthesis. Overall, this work establishes a sustainable, scalable, and cost-effective route for zeolite defect healing and provides a general strategy to overcome the long-standing transport-decomposition trade-off in tandem catalysis with in situ-generated H2O2.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"33 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210453","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":"Hidden Truchet Architecture\u0000in Zinc\u0000 p\u0000 -Hydroxybenzoate","authors":"Hunter J. Windsor,Guy Greenbaum,Tristan N. Dolling,Yevheniia Kholina,Andrew L. Goodwin","doi":"10.1021/jacs.6c15350","DOIUrl":"https://doi.org/10.1021/jacs.6c15350","url":null,"abstract":"Abstract We redetermine the structure of the disordered metal–organic framework Zn(hba) (hba2– = the dianion of 4-hydroxybenzoic acid). Using single-crystal X-ray diffraction measurements, we characterize the structured diffuse scattering that is experimentally observed for this material and which is characteristic of strongly correlated disorder. We use geometric and crystal-chemical arguments to propose a general model for correlated disorder in Zn(hba), and then relate this model to a specific realization of so-called Truchet tilings. Using Monte Carlo simulations, we proceed to show that the model so developed is simultaneously consistent with both the average crystal structure solution described previously and the structured diffuse scattering reported here. The existence of ordered analogues with different but related chemistry suggests scope for control over correlated disorder in this family of metal–organic frameworks. Our study illustrates the potential for a Truchet-tile formalism to help describe and understand more generally the correlated disorder that can occur in network structures.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"169 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210409","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 High-Nickel\u0000Cathode Material for Lithium-Ion Batteries\u0000Integrating a Proposed 3D Ionic Percolation Network and Interwoven\u0000Layered/Rock-Salt Nanodomains","authors":"Jun Wang,Yan Zhao,Jinxiang Fan,Xincheng Lei,Ting Liu,Juping Xu,Huaican Chen,Sijie Guo,Zhiliang Hu,Quanzhi Yu,Sidong Zhang,Yuanguang Xia,Bing Huang,Dong Su,An-Min Cao,Wen Yin","doi":"10.1021/jacs.6c14375","DOIUrl":"https://doi.org/10.1021/jacs.6c14375","url":null,"abstract":"Abstract High-nickel single-crystal cathodes effectively address the poor mechanical stability and severe side reactions that plague their polycrystalline counterparts. However, they introduce new structural challenges, including extended Li+ diffusion pathways, which in turn lead to structural slips, lattice distortions, and phase transformations, ultimately compromising both electrochemical capacity and structural stability. Herein, we report a state-of-the-art cathode architecture for high-nickel materials, derived from high-energy neutron irradiation of single-crystal LiNi0.92Co0.06Mn0.02O2 particles. This process induces long-range Li/Ni antisite disorder and short-range metal–oxygen octahedral distortions, concurrently yielding a nanostructure of abundant grain boundaries and interwoven layered/rock-salt nanodomains within the single-crystalline particles. These grain boundaries are proposed to constitute a 3D percolation network for rapid Li+ transport, whereas the interwoven nanodomains may act as local structural reinforcing units that help suppress irreversible phase transitions and the propagation of interfacial side reactions during cycling. These characteristics are favorable for sustaining continuous Li+ deintercalation/intercalation and reversible electrochemistry, thereby preserving the structural stability of the single-crystal framework while simultaneously shortening diffusion pathways. As a result, the engineered cathode delivers a high specific discharge capacity of 213.9 mAh/g at 0.2 C and 152.2 mAh/g at 10 C (within 4.5 V). Moreover, it retains 80.0% of its initial capacity after 450 cycles at 5 C, significantly outperforming the reference single-crystal cathode (64.2%). This work establishes high-energy neutron irradiation as an effective cathode reconstruction strategy, offering a viable route toward robust, high-energy cathodes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"63 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210406","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":"Surface-Layer Pore\u0000Aperture Engineering in a Metal–Organic\u0000Framework for High-Capacity CO2/C2H2 Molecular Sieving","authors":"Muzi Li,Yingjie Wang,Xin Zhang,Xuefeng Bai,Lu Liu,Jianyun Li,Lin-Hua Xie,Jian-Rong Li","doi":"10.1021/jacs.6c14696","DOIUrl":"https://doi.org/10.1021/jacs.6c14696","url":null,"abstract":"Abstract Molecular sieving in metal–organic frameworks (MOFs) is commonly achieved by narrowing the entire pore network, which enhances size exclusion but often sacrifices adsorption capacity. Here we report surface-layer pore aperture engineering as a spatially decoupled strategy for high-capacity CO2/C2H2 molecular sieving. Through surface-confined coordination modification of a copper-based MOF, the external pore apertures were selectively regulated while the internal adsorption space was largely preserved. Microscopy, elemental mapping, depth-resolved XPS, and X-ray absorption spectroscopy support the formation of a surface-confined functional shell at the pore aperture. The modified framework converts a nonselective, high-capacity adsorbent into a CO2/C2H2 molecular sieve. BUT-169-NH2-TRZ retains a high CO2 uptake of 90.3 cm3 g–1 at 298 K and 1 bar while suppressing C2H2 adsorption to 2.7 cm3 g–1, representing a new benchmark for CO2/C2H2 sieving separation. Further optimization with hexylamine affords faster CO2 transport and dynamic CO2/C2H2 separation, delivering a high productivity of 1.13 mol kg–1 for C2H2 (purity > 99.99%) over repeated breakthrough cycles. This work establishes surface-layer pore aperture engineering as a route to overcome the conventional selectivity–capacity trade-off in molecular sieving separations.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"25 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210405","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":"Stable Open-Shell Bowl-Shaped\u0000Cycloarene with Multiple\u0000Hybrid Spin–Spin Coupling and Tunable Radical Characters","authors":"Yuanhe Gu,Dongyue An,Tong Shen,Ya Zou,Rong Zhang,Jiangyu Zhu,Teng Wang,Jishan Wu,Yunqi Liu,Xuefeng Lu","doi":"10.1021/jacs.6c13049","DOIUrl":"https://doi.org/10.1021/jacs.6c13049","url":null,"abstract":"Abstract The precise syntheses of well-defined cycloarenes and stable open-shell polyradicaloids are two challenging topics in chemistry and materials science. Herein, the first example of a cycloarene polyradicaloid molecule (CPR) with three types of adjacent spin–spin coupling was successfully synthesized in single-crystal form by fusing Chichibabin, Schlenk, and o-quinodimethane hydrocarbons into a conjugated double-stranded bowl structure. It exhibits a small singlet–triplet energy gap, significant polyradical characters, and remarkable stability (t1/2 = 110 days in air-saturated solution). Interestingly, CPR adapts a rigid oval-bowl-shaped configuration and demonstrates fascinating encapsulation of fullerenes C60 and C70. Crucially, various experimental results confirm that the intramolecular spin–spin interactions can be effectively modulated by an electron-accepting guest, which represents the first systematic study of the radical characters in π-conjugated polyradicaloids by a supramolecular assembly strategy. Our findings provide a new approach for constructing stable cycloarene polyradicaloids and a novel strategy for manipulating radical spin coupling.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210448","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":"Cu–N3 Single-Atom Catalysts Enable\u0000High-Turnover C–N and C–O Cross-Coupling of Aryl Electrophiles","authors":"Liang Ge,Jianguo Chen,Nan Song,Jiarui Jiang,Zaibin Xue,Mingkai Liu,Yu Tang,Jie Zeng","doi":"10.1021/jacs.6c14402","DOIUrl":"https://doi.org/10.1021/jacs.6c14402","url":null,"abstract":"Abstract Transition-metal-catalyzed C–N cross-coupling is fundamental to the synthesis of pharmaceuticals, agrochemicals, and functional materials. However, many copper-based catalytic systems rely on exogenous molecular ligands to establish and tune the coordination environment around copper centers, which can increase catalyst-design complexity and complicate catalyst recovery and reuse. We report a copper single-atom catalyst (Cu–N3/OMC) that enables ligand-free C–N and C–O cross-coupling of aryl electrophiles, with isolated Cu sites embedded in a nitrogen-doped carbon framework that provides an intrinsic coordination environment. This system enables ligand-free copper-catalyzed C–N coupling of synthetically relevant aryl bromides and further extends the reaction to less-activated aryl chlorides. A broad range of substituted aryl and heteroaryl bromides─including electron-rich, electron-deficient, ortho-substituted, and fused substrates─undergo efficient coupling with diverse amines and alcohols, affording the corresponding products in moderate to excellent yields (up to 96%). Selected aryl chlorides are also compatible under KI-promoted conditions, albeit with reduced efficiency in some cases. The methodology is applicable to late-stage functionalization of complex pharmaceutical molecules and can be conducted on a preparative scale (5–100 mmol), affording yields of 90–95% and TONs of up to 84,000 under air. TON values were calculated based on the total Cu loading. More broadly, this work suggests that support-engineered coordination environments can influence the reactivity of isolated Cu sites, providing a strategy for ligand-free heteroatom cross-coupling.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"89 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210454","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":"Pd(II)-Templated End-to-End\u0000Cyclization of Doubly\u0000N-Confused Bilatrienes: A Stable Singlet Diradicaloid Dye with\u0000Efficient Absorption across the Solar Spectrum","authors":"Aninda Ghosh,Sandipa Bhandari,Shigeki Mori,Daiki Shimizu,Takahisa Ikeue,Hiroyuki Furuta,Masatoshi Ishida","doi":"10.1021/jacs.6c12833","DOIUrl":"https://doi.org/10.1021/jacs.6c12833","url":null,"abstract":"Abstract We report a highly stable singlet diradicaloid (Pd1-dimer), formed through a Pd(II)-templated end-to-end cyclization of a linear N-confused bilatriene (1). This unique Pd-bridged double-loop complex exhibits an open-shell singlet diradicaloid ground state with an extremely narrow energy gap. Interestingly, further coordination of Pd(II) at the NNCC core generates a distinct doublet radicaloid species (Pd21-dimer). Despite their open-shell electronic nature, both complexes exhibit remarkable stability under ambient conditions and reversible redox interconversion between their corresponding charged states. The complexes display broad visible-to-second near-infrared (NIR-II) absorption profiles arising from extremely narrow energy gaps. Efficient nonradiative relaxation associated with the open-shell electronic structure enables strong photothermal conversion, and Pd1-dimer exhibits a photothermal conversion efficiency of 47.8% in aqueous nanoparticle dispersions under 940 nm laser irradiation. Moreover, when integrated into a carbon nanotube-modified photothermal conversion membrane, applying a small amount of Pd1-dimer (e.g., 1.0 mg per membrane) yields a solar-to-vapor conversion efficiency of 84.4% and an evaporation rate of 1.22 kg m–2 h–1 under 1.0-sun irradiation. This work establishes open-shell porphyrinoid diradicaloids as a promising molecular platform for efficient solar-thermal energy conversion and interfacial seawater desalination.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"53 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210450","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}