Journal of the American Chemical Society最新文献

{"title":"Dynamic Nonlinear Effects in the Asymmetric Kinetic Resolution Polymerization of Racemic Diazoacetates to One-Handed Helical Polycarbenes","authors":"Xun-Hui Xu,Shu-Ming Kang,Jiaqi Yu,Jie Zhang,Xinhua Wan","doi":"10.1021/jacs.6c10680","DOIUrl":"https://doi.org/10.1021/jacs.6c10680","url":null,"abstract":"The asymmetric kinetic resolution polymerization (AKRP) of racemic diazoacetates mediated by a [Rh(cod)Cl]2/chiral amine dual catalyst system exhibits dynamic nonlinear effects (DNLEs) in the relative rate constant (Krel). The overall Krel increases nonlinearly with the monomer conversion during polymer chain propagation and reaches a plateau at a medium conversion. These DNLEs originate from synergistic chirality amplification between the catalytic chain end and the evolving helical conformation of the growing polymer chain. Under optimized conditions, Krel increases from 15 at 3% monomer conversion to ∼ 138 at 33% conversion, and then reaches a plateau. The steric bulk of both the pendant groups of monomers and the chiral amine ligand critically regulates the magnitude and evolution of DNLEs, and reducing this bulk leads to a pronounced decrease in Krel. Chain extension experiments using the preformed helical macroinitiators exhibited a constant Krel, confirming that a well-formed helical conformation maintains stable enantioselectivity for AKRP. Computational studies further revealed that, during chain propagation, decameric species with well-developed helical conformations exhibit more pronounced energy differences between the R- and S-enantiomers than the corresponding initial monomer-inserted species. These results suggest that the one-handed helical conformation is associated with the enhanced enantiomer recognition at the catalytic center. This study reveals DNLEs in AKRP in which enantioselectivity evolves nonlinearly during polymer chain propagation, highlighting a dynamic chiral amplification mechanism that can surpass the intrinsic selectivity of a static catalyst through the cooperative action of chiral chain ends and helical conformation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"75 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374786","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":"Zeolite-Confined Triatomic Cu Oxides at Silanol Nests as Hydrogen Transport Channels for H2 Production from Methanol Steam Reforming","authors":"Yongbin Yao,Maoshuai Jiang,Fan Wang,Ligang Zhang,Rudong Liu,Shihao Wang,Kuo Liu,Tao Zhang","doi":"10.1021/jacs.6c15075","DOIUrl":"https://doi.org/10.1021/jacs.6c15075","url":null,"abstract":"Cu-based catalysts offer high methanol steam reforming (MSR) activity but are limited by unstable Cu+–Cu0 interconversions due to the redox and sintering labilities of Cu. Herein, we developed a universal amino-functionalized “gripper” strategy for firmly and precisely anchoring atomically dispersed metals (e.g., Cu, Co, Ni) within Beta-zeolite. Triatomic Cu oxide (Cu3Ox) sites lower the methanol dehydrogenation activation barrier, and the synergistic interplay with adjacent OH groups from silanol nests accelerates H2 evolution and the MSR reaction. Spatially decoupling Cu-mediated methanol activation from silanol-driven H2 evolution at silanol nests as proton transport channels within the confining zeolite framework also effectively protected Cu from sintering, achieving a high specific activity of 951 molH2·molCu–1·h–1 and over 600 h of stability under continuous regeneration. This work provides a universal strategy for synthesizing atomically dispersed metal catalysts and a new design principle for maintaining the Cu structure during MSR.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"277 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374792","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":"Dye-Sensitization Enables Visible-Light-Driven N–N Bond Cleavage in a Dinuclear Rhenium Dinitrogen Complex","authors":"Limei Tian,Zijian Zhao,Tian-Lin Zhang,Yun-Shu Cui,Dan-Dan Zhai,Weijian Yang,Jing-Ao Fan,Pengju Li,Matthew J. Goodwin,Tinghao Wu,Zhang-Jie Shi,Chi Zhang,Gerald J. Meyer,Ke Hu","doi":"10.1021/jacs.6c10170","DOIUrl":"https://doi.org/10.1021/jacs.6c10170","url":null,"abstract":"Conversion of μ-N2 complexes into nitrogenous compounds is one of the most important and challenging chemical transformations in N2 fixation. Although photochemical N2 splitting has been demonstrated, existing approaches predominantly rely on high-energy ultraviolet light that generally affords low efficiency and poor selectivity. Herein, we establish a visible-light-driven molecular photosensitization strategy that enables efficient and selective N–N bond cleavage in a dinuclear rhenium dinitrogen complex. Blue light excitation of the organic photosensitizer 4DPAIPN (2,4,5,6-tetrakis(diphenylamino)isophthalonitrile) is shown to initiate N–N scission to afford the corresponding rhenium nitride in 96% yield. Kinetic analysis of nanosecond transient absorption data through the Balzani-Scandola model indicates energy transfer from the photosensitizer to an acceptor state that lies approximately 2.31 eV above the ground state of the μ-N2-bridged dirhenium complex. This photosensitization strategy decouples light harvesting from N–N bond activation, eliminates the need for UV light, and shows broad applicability across different visible-light absorbing photosensitizers, including transition metal complexes and organic chromophores with long-lived, high-energy triplet excited-states. These findings establish dye-sensitization as a powerful strategy for visible-light-driven N–N bond cleavage for mechanistic study and the future realization of a photochemical pathway for nitrogen fixation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"20 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374776","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":"Dynamic Metal Encapsulation in a Pt/TiOx system Regulated by Pt-Assisted TiO2 Amorphization","authors":"Dongxiao Chen,Qian-Yu Liu,Cheng Shang,Zhi-Pan Liu","doi":"10.1021/jacs.6c19944","DOIUrl":"https://doi.org/10.1021/jacs.6c19944","url":null,"abstract":"Strong metal–support interaction (SMSI) plays an important role in heterogeneous catalysis, but remains poorly understood, particularly on the origin of SMSI under an oxidative atmosphere. Hereby grand canonical structure exploration of over 4 million bulk PtTi alloys and Pt or PtTi-supported Ti oxide (TiOx) surface structure candidates, we resolve the Pt/TiOx system, a text-book example of SMSI, under both reductive and oxidative conditions: it experiences an encapsulation─deep encapsulation─decapsulation dynamic reconstruction under a sequence of H2 reduction─O2 oxidation─H2 plus O2 redox thermal treatment. The whole process was kinetically simulated by long-time (69 ns) molecular dynamics simulations, revealing in detail how a 3 nm Pt nanoparticle undergoes nonclassical SMSI under an oxidative and redox atmosphere. We find that Pt-assisted TiO2 amorphization is the key to the transition of various SMSI states at different conditions, which elevates Ti chemical potential via amorphization toward low-coordinated [TiO4]. Finally, explainable machine learning models were developed to predict nonclassical SMSI cases and clarify their rarity in nature.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"19 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374775","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":"Tailoring Solid-State Reaction Pathways for Bulk Fluorination of Mn-Rich Rock-Salt Cathodes","authors":"Venkata Sai Avvaru,Nathan J. Szymanski,Seonghun Jeong,Meredith Goudreau,Martin Kunz,Mateusz Zuba,Ozgenur Kahvecioglu,Noah Taebin Lee,Meghan Shen,Mary C. Scott,Christopher J. Bartel,Haegyeom Kim","doi":"10.1021/jacs.6c15586","DOIUrl":"https://doi.org/10.1021/jacs.6c15586","url":null,"abstract":"Manganese-based cation-disordered rock-salt (DRX) cathodes offer high capacities without relying on cobalt and nickel, but maintaining that capacity over extended cycling often requires bulk fluorination. The challenge is that incorporating fluorine into Mn-rich DRX host structures is hindered by unfavorable thermodynamics and the stability of LiF, often necessitating elevated synthesis temperatures that promote severe lithium and fluorine volatilization. This study overcomes that limitation by manipulating the solid-state reaction pathway using unconventional Li6MnO4 and MnF2 precursors in a challenging Mn-rich model system (Li1.2Mn0.6Ti0.2O2–xFx). This precursor engineering strategy reshapes the thermodynamic landscape. Computational modeling and in situ X-ray diffraction reveal that by using reactive starting materials, we suppress the crystallization of less reactive intermediates, enabling bulk fluorination at a lower temperature. The resulting DRX retains both a high fluorine content and the lithium excess required for three-dimensional percolation, delivering improved electrochemical performance relative to material synthesized from conventional precursors.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"27 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374782","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":"Programming Oxygen Reduction Selectivity via Peroxo Basicity: Acid-Controlled 2e–/4e– Reduction Switching at a Dicobalt Platform","authors":"Kai Hua,Yu-Hua Guo,Ming-Tian Zhang","doi":"10.1021/jacs.6c17908","DOIUrl":"https://doi.org/10.1021/jacs.6c17908","url":null,"abstract":"Achieving switchable 2e–/4e– oxygen reduction selectivity within a single molecular catalyst remains an unmet challenge because the key metal–oxygen intermediate typically commits to one pathway. Herein, we demonstrate that this limitation can be overcome by elevating the basicity of the peroxo intermediate to a level where both proton-transfer (PT) and proton-coupled electron transfer (PCET) manifolds become accessible, with the dominant pathway dictated solely by the external acid strength. A dicobalt μ-1,2-peroxo complex supported by an electron-rich macrocyclic poly-NHC ligand exhibits a computed pKa1 of ∼8.8, placing it in a unique thermodynamic window. Stoichiometric protonation bifurcates cleanly: strong acids (HClO4) trigger rapid diprotonation to release H2O2, whereas weak acids (Et3NHOTf) promote O–O bond cleavage to afford a μ-hydroxo complex. Under catalytic conditions, this dichotomy translates into complete selectivity switching─100% H2O2 with HClO4 versus 90% H2O with Et3NHOTf, accompanied by a switch in the rate-determining step from O2 binding to PCET (KIE = 1.60). Crucially, a structurally analogous but less basic peroxo complex predictably inverts the selectivity to H2O under identical conditions, providing a closed-loop validation of the basicity-selectivity relationship. These results establish intermediate basicity as a general, tunable design parameter for programming product selectivity in multielectron catalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"31 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374791","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":"Porphyrin-Driven Redox Tuning in Structurally Defined De Novo Heme Proteins","authors":"Cameron Mellor,Christopher Williams,Ethan L. Bungay,Jessica C. Berrones-Reyes,Rob Barringer,Catherine R. Back,Paul Molinaro,Shakir A. Siddiqui,Alexandra N. Stuart,Thomas A. A. Oliver,Ronald L. Koder,Bruce R. Lichtenstein,Adrian J. Mulholland,Matthew P. Crump,J. L. Ross Anderson","doi":"10.1021/jacs.6c11808","DOIUrl":"https://doi.org/10.1021/jacs.6c11808","url":null,"abstract":"Designing redox proteins with predictable and tunable electron transfer properties is a major goal in de novo bioenergetics. Here we show that replacing heme B with a series of structurally conservative non-natural metalloporphyrins enables broad modulation of redox potentials over 400 mV in the de novo designed monoheme m4D2 and diheme 4D2 T19D. The non-natural porphyrins bind with high affinity and do not compromise either the heme binding site or global protein structure, as evidenced by X-ray crystallography and NMR spectroscopy. We also report the native-like NMR structure of m4D2 loaded with the non-natural and symmetric iron 2,4-dimethyldeuteroporphyrin IX, confirming our modular approach to tetrahelical redox protein design. This work establishes a versatile platform for constructing tunable electron carriers for engineered bioenergetic pathways and bioelectronic applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"7 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374778","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":"Dynamic Acidic Adsorbates Govern Fast Oxygen Incorporation in Ceria through Interfacial Electrostatics","authors":"Francesco Chiabrera,Kosova Kreka,Federico Baiutti,Burcu Karagoz,Marlene Anzengruber,Juan Carlos González-Rosillo,Matthijs Van Spronsen,Albert Tarancón","doi":"10.1021/jacs.6c11743","DOIUrl":"https://doi.org/10.1021/jacs.6c11743","url":null,"abstract":"The oxygen reduction reaction (ORR) is a key heterogeneous process underpinning energy conversion, catalytic, and sensing technologies. However, reported ORR kinetics at oxide surfaces often vary widely because surface chemistry evolves under operating conditions. Ceria-based fluorites have been proposed as protective layers to stabilize perovskite electrodes, but ORR kinetics are typically considered sluggish and reported values have large variability. Herein, we demonstrate that cathodic polarization triggers an unexpected activation in Gd-doped ceria (CGO) dense thin films at 500 °C, enabling oxygen incorporation rates that surpass state-of-the-art materials such as La0.5Sr0.5FeO3−δ and approach the performance of La0.6Sr0.4CoO3−δ. Operando near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS), supported by ex situ surface-sensitive tip-enhanced Raman spectroscopy (TERS), reveals that CGO surface activation coincides with a reversible, overpotential-dependent modulation of sulfate adsorbates. Integration of these measurements with nondilute space-charge modeling suggests that charged adsorbates dynamically tune the near-surface electrostatic potential and electron concentration, thereby controlling oxygen incorporation kinetics. These results support adsorbate-induced electrostatic effects as a key mechanism in ceria and show that ORR kinetics are dynamically set by surface chemistry under operation, rather than by intrinsic bulk defect chemistry alone.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"16 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374779","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":"Multiphase Inorganic-Rich Interphases with Integrated Li-Ion Capture-Transport Ability for High-Rate Lithium Metal Batteries","authors":"Likun Chen,Tian Gu,Zhuo Han,Wenting Cui,Jinshuo Mi,Xufei An,Ke Yang,Jiabin Ma,Liang Zhao,Jie Biao,Yuhang Li,Guanyou Xiao,Hao Guo,Tingzheng Hou,Bing Han,Ming Liu,Yan-Bing He","doi":"10.1021/jacs.6c11241","DOIUrl":"https://doi.org/10.1021/jacs.6c11241","url":null,"abstract":"Lithium metal batteries promise high-energy-density storage but are limited by unstable solid–electrolyte interphases, which couple poor passivation, sluggish Li+ transport, dendritic deposition, and safety risks. Herein, we report a multiphase inorganic-rich solid–electrolyte interphase (m-SEI) containing P- and Al-derived species including Li3P, LiAl5O8, Li3PO4, and Li2Al, which is formed from the in situ reaction between a flame-retardant aluminum diethyl hypophosphite (ADP) interlayer and lithium metal. This multicomponent inorganic SEI enables an integrated capture-transport mechanism by combining high Li+ affinity, facilitated desolvation, and low-barrier Li+ migration pathways in individual inorganic phases and their heterophase interfaces, thereby facilitating rapid Li+ interfacial migration. Its chemical inertness and high Young’s modulus of 17.14 GPa further suppress electrolyte decomposition and Li dendrite growth. As a result, the Li-metal batteries with m-SEI deliver an extended lifespan of 1000 h at a high current density of 4 mA cm–2. Li||NCM811 full cells with a high cathode loading (20 mg cm–2) and ultrathin Li foil (50 μm) retain 80% capacity after 250 cycles, while Li||NCM811 pouch cells retain 90% capacity after 500 cycles. This work establishes the capture-transport mechanism as an effective design principle for regulating Li+ interfacial dynamics and offers a practical interphase-engineering strategy for constructing ion-conductive and chemically protective interphases in durable lithium metal batteries.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"32 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374781","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":"Efficient Long-Wavelength Through-Space Charge-Transfer Thermally Activated Delayed Fluorescence in Conformationally Adaptive Emitters without Conformational Locking","authors":"Nae Aota,Jaijanarthanan Lingagouder,Nuno Gandum,Leonardo Evaristo de Sousa,Lucy A. Weatherill,Marc K. Etherington,Norimitsu Tohnai,Satoshi Minakata,Piotr de Silva,Przemyslaw Data,Youhei Takeda","doi":"10.1021/jacs.6c12459","DOIUrl":"https://doi.org/10.1021/jacs.6c12459","url":null,"abstract":"Through-space charge-transfer thermally activated delayed fluorescence (TSCT-TADF) emitters often employ conformationally constrained donor–acceptor architectures to control through-space electronic coupling, particularly for long-wavelength emission. Here, we report conformationally adaptive orange-to-red TSCT-TADF emitters based on an S-shaped donor−π–acceptor−π–donor framework composed of phenoxazine donors, xanthene linkers, and a dibenzo[a,j]phenazine acceptor. Structural and NMR analyses reveal substantial conformational mobility, while systematic conformational searches and excited-state calculations identify thermally accessible conformers with distinct donor–acceptor geometries and excited-state characteristics. Comparative studies with reference compounds and fragment-resolved transition-density analysis show that the xanthene linker primarily acts as a conformational regulator and that the low-energy CT states have predominant TSCT character with only minor linker involvement. Temperature-dependent early-time photoluminescence measurements reveal continuous spectral relaxation in fluid toluene that slows upon cooling and is absent in rigid Zeonex and mCBP hosts, providing strong evidence for structural relaxation following photoexcitation within a pre-existing conformational ensemble. The emitters exhibit orange-to-red TADF with reverse intersystem crossing rates on the order of 105–106 s–1. Organic light-emitting diodes employing these emitters show electroluminescence at 598–624 nm, external quantum efficiencies up to 14.9%, and limited efficiency roll-off over a broad luminance range. These results demonstrate that efficient long-wavelength TSCT-TADF can be realized without permanent conformational locking and establish a framework for understanding the interplay between ground-state conformational heterogeneity and excited-state structural relaxation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"14 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374784","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}