Journal of the American Chemical Society最新文献

{"title":"Surface-Controlled TiO2 Nanocrystals with Catalytically Active Single-Site Co Incorporation for the Oxygen Evolution Reaction","authors":"Chang Liu, Soonho Kwon, Perrin Godbold, Grayson Johnson, Sooyeon Hwang, Chengjun Sun, Hua Zhou, William A. Goddard, III, Sen Zhang","doi":"10.1021/jacs.5c05795","DOIUrl":"https://doi.org/10.1021/jacs.5c05795","url":null,"abstract":"The design of advanced electrocatalysts is often hindered by uncertainties in identifying and controlling the active surfaces and catalytic centers within heterogeneous materials. Here we present the synthesis of single-site Co catalysts, substitutionally doped into surface-controlled TiO₂ anatase nanocrystals, aimed at enhancing the oxygen evolution reaction (OER). Grand canonical quantum mechanics calculations reveal that the kinetics of the OER, following an adsorbate evolution mechanism, is markedly influenced by the coordination environment of Co. The simulations suggest significantly higher turnover frequencies when Co is doped into the (001) surface of TiO₂ compared to the (101) surface. Consistent with the computational findings, experimental results show that Co-doped TiO₂ (Co-TiO₂) nanoplates with selectively exposed {001} surfaces exhibit enhanced current densities and turnover frequencies compared to Co-TiO₂ nanobipyramids with {101} surfaces. This study highlights the synergy between theoretical calculations and precision synthesis in the development of more effective catalysts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"5 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146300","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":"Enhanced THz Emission and Chirality Control in van der Waals Ferromagnetic FePd2Te2/Pt Heterostructures","authors":"Jiali Zhang, Bingxian Shi, Haoran Xu, Yiwen Song, Yuqing Zou, Ziyang Li, Hongtao Dai, Yuna Song, Qingyuan Jin, Peng Cheng, Zuanming Jin, Zongzhi Zhang","doi":"10.1021/jacs.5c04284","DOIUrl":"https://doi.org/10.1021/jacs.5c04284","url":null,"abstract":"Two-dimensional (2D) magnetic materials, with their unique van der Waals (vdW) layered structure, tunable magnetism, and strong spin–orbit coupling, are promising for spintronic applications like terahertz (THz) emitters. Our study investigates the THz radiation properties of the newly discovered vdW ferromagnet FePd₂Te₂, which features a one-dimensional Fe zigzag chain structure and strong in-plane uniaxial anisotropy. Using ultrafast reflective THz emission spectroscopy (TES), we demonstrate that the paramagnetic FePd₂Te₂ produces weak THz emission at room temperature. However, when capped with a 3 nm Pt layer, the THz emission intensity is significantly enhanced, attributed to spin-to-charge conversion (SCC) via the inverse spin Hall effect (ISHE). In the FePd₂Te₂/Pt heterostructure, the THz emission intensity is closely linked to the spin texture induced by crystal twinning in FePd₂Te₂ and depends on the polarization angle of the pump laser. Two mechanisms for the photoexcited spin current generation are identified: one from spin-polarized hot electrons at the FePd₂Te₂/Pt interface, and the other, which is dominant, from angular momentum transfer through a nonlinear optical effect that induces impulsive magnetization. These findings provide valuable insights into the spin dynamics of 2D materials and open avenues for high-density, low-power THz spintronic device development based on advanced 2D vdW magnets.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"134 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144154173","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":"Concentration-Driven Ring Expansion Metathesis Polymerization via Tunable Ring Transfer Processes","authors":"Meredith N. Pomfret, Nicholas P. Serck, Lucy P. Miller, Matthew R. Golder","doi":"10.1021/jacs.5c05347","DOIUrl":"https://doi.org/10.1021/jacs.5c05347","url":null,"abstract":"Ring expansion metathesis polymerization (REMP) is a robust and versatile method used to access polymeric cyclic architectures for applications in biomedicine, electronics, and performance engineering. Cyclic Ru-benzylidene REMP catalyst <b>CB6</b> demonstrates higher stability and polymerization rates compared to other Ru-based systems. However, <b>CB6</b> also exhibits an unusual molar mass evolution profile where high-molar-mass cyclic polymers are produced at early time points followed by a gradual decrease in molar mass. For broad cyclic polymer applications to be fully realized, a mechanistic understanding of REMP is crucial. In this work, we investigate the polymerization profiles of <b>CB6</b> using a series of mechanistic studies to probe the requisite ring transfer steps envisaged for such a polymerization profile. Furthermore, our studies reveal an intricate relationship between reaction concentration and experimental molar mass. These collective studies demonstrate <b>CB6</b>’s role not only as an initiator but also as a catalytic ring transfer agent. Overall, we showcase a new toolkit by which to control REMP that will allow further optimization of catalyst design and the creation of novel cyclic materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"80 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146299","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":"Tunable Self-Assembly of Decanuclear Ni(II) Carbonato Clusters with a Hydroxyquinolinato Shell: Robust Porous Networks with Reversible Solvent-/Temperature-Driven Phase Transitions and Selective Gas Separation","authors":"Katarzyna Sołtys-Brzostek, Kamil Sokołowski, Iwona Justyniak, Aurelia Li, David Fairen-Jimenez, Alicja Supeł, Michał Terlecki, Janusz Lewiński","doi":"10.1021/jacs.5c04096","DOIUrl":"https://doi.org/10.1021/jacs.5c04096","url":null,"abstract":"The utilization of molecular metal clusters as building units of noncovalent porous materials (NPMs) is a promising strategy, combining the versatile functionality of organic and inorganic subunits with the softness and flexibility of molecular solids controlled by noncovalent interactions. However, the development of robust porous functional frameworks based on self-assembly driven by noncovalent forces is still highly challenging. Herein, we report the synthesis and characterization of a discrete decanuclear Ni(II) hydroxyquinolinato-carbonato cluster, [Ni₁₀(μ₆-CO₃)₄(L)₁₂], which, depending on the crystallization conditions, self-assembles into either of two microporous frameworks: diamondoid <b>WUT-1(Ni)</b> and pyrite <b>WUT-2(Ni)</b>. The transitions between both polymorphs can also be selectively triggered by temperature or exposure to vapors of a particular organic solvent, which is accompanied by the easy recovery of crystallinity by the materials from the noncrystalline phase. Moreover, both materials show excellent robustness toward various chemical environments, including air/moisture and water stability, and demonstrate interesting gas adsorption properties. Remarkably, <b>WUT-1(Ni)</b> exhibits significant enhancement in gas uptake compared to the previously reported isostructural Zn(II) analogue, <b>WUT-1(Zn)</b>, representing one of the highest H₂ uptakes among NPMs. In turn, tighter voids of the ultramicroporous <b>WUT-2(Ni)</b> framework facilitate selective interactions with gas molecules, resulting in outstanding selectivity in the adsorption of CO₂ over CH₄ and N₂. The presented studies demonstrate the profound role of the character of metal centers on the self-assembly of isostructural nanoclusters as well as properties of the resulting microporous frameworks.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"2 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146268","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":"An Ethynyl-Linked sp-Carbon-Conjugated Covalent Organic Framework through Sonogashira Cross-Coupling Reactions","authors":"Hao Yang, Shanshan Tao, Shuyue He, Donglin Jiang","doi":"10.1021/jacs.5c01709","DOIUrl":"https://doi.org/10.1021/jacs.5c01709","url":null,"abstract":"We report the synthesis of ethynyl-linked covalent organic frameworks through microinterfacial polymerization with Sonogashira cross-coupling reactions of 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin (TEPP) and 5,10,15,20-tetrakis(4-bromophenyl)porphyrin (TBPP). This framework consists of extended two-dimensional tetragonal layers with porphyrin knots and ethynyl (−C≡C−) linkers and constitutes layered frameworks with an AB-stacking mode, creating periodically ordered porphyrin arrays and one-dimensional microporous channels. The ethynyl-linked porphyrin framework features a broad absorption spectrum that covers the entire visible region and extends to the infrared zone exceeding 1400 nm, exhibits a low optical bandgap of 1.32 eV, and is photoconductive, generating prominent photocurrent. The micropores formed by the AB stacking are highly accessible, enabling iodine uptake, CO₂ capture, and Li⁺ confinement. Remarkably, the Li⁺-confined frameworks exhibit Li⁺ conductivity of 2.1 × 10^–5 S cm^–1 at 100 °C under anhydrous conditions and achieve an exceptional Li⁺ conductivity of 3.9 × 10^–3 S cm^–1 at a relative humidity of 98%. Temperature-dependent experiments revealed that Li⁺ conduction is facilitated by a low-energy barrier hopping mechanism. We envision that our ethynyl linkage strategy will not only develop novel sp-carbon-conjugated frameworks but also enable unprecedented functions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"58 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146294","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":"Non-Aqueous Binary and Ternary nHF·Base Fluoride Reagents: Characterization of Structure, Properties, and Reactivity","authors":"Stephen G. Sweeting, Alastair J. J. Lennox","doi":"10.1021/jacs.5c05472","DOIUrl":"https://doi.org/10.1021/jacs.5c05472","url":null,"abstract":"Binary and ternary <i>n</i>HF·base mixtures are an important class of nucleophilic fluorinating reagents used in myriad fluorination reactions. These reagents are soluble in organic media, and by varying <i>n</i>, the reactivity of fluoride can be controlled and tuned. Of particularly frequent utility are the ternary mixtures of <i>n</i>HF·amine, in which the binary 9HF·py and 3HF·NEt₃ mixtures are combined, the ratio (<i>n</i>) of which has a strong influence on the reaction yields and selectivity. The structure, properties, and reactivity of these non-aqueous ionic liquid mixtures vary considerably with <i>n</i>. Herein, we disclose a combined experimental and theoretical study aimed at characterizing binary and ternary <i>n</i>HF·base mixtures. We have measured the concentration of components, their Hammett acidity <i>H</i>₀, nucleophilicity, and basicity, while using theory to calculate the lowest energy size and structure of the clusters formed at different ratios of HF to base and analyzed the noncovalent interactions present. The quantification of properties and enhanced understanding presented should facilitate the further development and use of this important family of fluorination reagents.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"45 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146304","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":"Photo- and Copper-Catalyzed Enantioselective Oxidation of Benzylic C(sp3)–H Bonds","authors":"Fu Li, Xian-Ming Liu, Jia-Bin Pan, Ling Dai, Yin Yang, Li-Jun Xiao, Chao Fan, Qi-Lin Zhou","doi":"10.1021/jacs.5c04142","DOIUrl":"https://doi.org/10.1021/jacs.5c04142","url":null,"abstract":"Here, we report a photo- and copper-catalyzed enantioselective oxidation of benzylic C(sp³)–H bonds using <i>N</i>-hydroxyphthalimide as the oxygenated reagent. The reaction proceeds under mild conditions and does not require excess substrates or oxidants. The oxidation products can be readily transformed into chiral benzylic alcohols or hydroxylamines. Preliminary mechanism studies suggest that the oxidation reaction proceeds via a free radical mechanism.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"51 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146320","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":"Hydrogen Bond Interaction Networks in the Mixed Pentamers of Hydrogen Sulfide and Water.","authors":"Pablo Pinacho,Cristóbal Pérez,Marcel Stahn,Rizalina T Saragi,Andreas Hansen,Stefan Grimme,Alberto Lesarri,Melanie Schnell","doi":"10.1021/jacs.4c18276","DOIUrl":"https://doi.org/10.1021/jacs.4c18276","url":null,"abstract":"The observation of gas-phase water clusters has been instrumental in understanding water aggregation and cooperativity, paving the way for solvation models in the bulk. However, the characterization of hydrogen sulfide self-aggregation is still largely unexplored. Here, we investigate two mixed pentamers of hydrogen sulfide and water to examine the influence of the weaker, dispersion-based and less directional interactions caused by hydrogen sulfide. Unprecedented structural resolution was obtained by combination of jet-cooled broadband rotational spectroscopy and quantum-chemical calculations. Specifically, we compare the 4:1 and 1:4 hydrogen sulfide - water pentamers, offering comparison with the prototype homoclusters. Important structural differences are revealed in the hydrogen sulfide clusters, which reorganize to compensate for the weaker sulfur-centered hydrogen bonds. The noncovalent interactions in the pentamers were rationalized using density functional theory and reduced electronic density calculations. Moreover, a comprehensive many-body decomposition energy analysis revealed significant variations in molecule two- and three-body contributions to the total interaction energy based on the relative proportions of H2O and H2S. These findings offer new insights into the distinct cooperative forces in water and hydrogen sulfide clusters. The results will improve our understanding and modeling of sulfur-centered hydrogen bonds, which may be useful across various research fields, including protein folding, molecular aggregation, materials science, and computational benchmarking.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144136802","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":"Herzberg Type-I or Type-II Predissociation Dynamics at the Conical Intersection: Bifurcation into Adiabatic or Nonadiabatic Pathway.","authors":"Kyung Chul Woo,Sang Kyu Kim","doi":"10.1021/jacs.5c03968","DOIUrl":"https://doi.org/10.1021/jacs.5c03968","url":null,"abstract":"Bifurcation dynamics into Herzberg type-I and type-II predissociation pathways at the conical intersection have been characterized in terms of their distinct reaction rates and energy-disposal dynamics from the picosecond time-resolved product state distributions measured at multiple S1/S2 vibronic states of thioanisole (C6H5SCH3). Electronic predissociation (type-I) occurs on a faster time scale and leads to the larger translational energies being released to the fragments (C6H5S• + •CH3) compared to the vibrational predissociation (type-II). While type-II dominates at the S1 zero-point level, the type-I quantum yield increases sharply near the S1/S2 conical intersection, which is consistent with the striking dynamic resonance observed for the reactive flux in the proximity of the conical intersection. Nonadiabatic product yield at the asymptotic limit was found to be enhanced predominantly through the type-I channel, suggesting that the quantum-mechanical nature of the reactive flux prepared near the first S1/S2 conical intersection is likely to be retained at the second S0/S2 conical intersection encountered in the later stage as there is little time to be altered during the ultrafast S-CH3 bond extension on the repulsive potential energy curve linking two conical intersections, enabling nonadiabatic control over product yields through the state-selection of the reactive flux.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"238 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144136814","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":"Electrodepositing Textured Sn Film as a Highly Reversible Anode for Aqueous Batteries.","authors":"Haozhe Zhang,Yanxia Yu,Diyu Xu,Minghao Zhang,Chen-Jui Huang,Jianxin Wang,Hao Liu,Fan Yang,Mingqian Li,Di-Jia Liu,Xihong Lu,Kang Xu,Ying Shirley Meng","doi":"10.1021/jacs.5c03861","DOIUrl":"https://doi.org/10.1021/jacs.5c03861","url":null,"abstract":"Electrodepositing metal materials in large capacity, at low potential, and with high reversibility serves as the foundation for any aqueous rechargeable battery chemistry to realize the promises of high energy, low cost, and high safety. However, such a foundation is not solid because of the natural tendency of metals to form irregular, nonplanar, and often dendritic morphologies during electrochemical crystallization, which is further amplified in an acidic environment due to the faster kinetics of the coupled proton and mass-transport processes between hydrated metal ions and free metal atoms. As a typical representative, tin metal (Sn0) has potential to achieve high energy in acidic batteries, but its nonuniform large-particle morphology, obtained from traditional electrodeposition, leads to dead Sn0 formation and deteriorating reversibility, accompanied by the sustained hydrogen evolution reaction (HER) and active Sn0 loss. Here, we report quaternary onium salts as effective interfacial cocations that, via selective adsorption, steadily texturize Sn0 deposition along the (211) plane, which is intrinsically inert to the HER, thus regulating the film deposition process by favoring the formation of planar Sn0 film. Such Sn0 film brings exceptional reversibility in acidic electrolytes, which translates into sustained cycling stability at applicable areal capacities in both anode-half cells (∼1500 deposition/dissolution cycles at 5 mAh cm-2) and full cells (350 charge/discharge cycles at 5 mAh cm-2). Textured electrodeposition with intrinsic HER-suppression capability provides a universal solution for diverse metal anode materials in rechargeable energy-dense aqueous batteries.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"6 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144136721","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}