Journal of the American Chemical Society最新文献

{"title":"Strain-Engineered Rh Single Atoms on Curved WS2 for Hydrogen Production and Coupled Photochemical Water Splitting.","authors":"Ting Gao,Jie Gu,Changheng Yang,Rui Wang,Chan Wang,Pengfei Zhang,Jiatong Li,Xiaoyan Zheng,Yunmiao Fan,Puheng Yang,Xiufu Hua,Junfeng Hui,Huigang Zhang","doi":"10.1021/jacs.5c04928","DOIUrl":"https://doi.org/10.1021/jacs.5c04928","url":null,"abstract":"Hydrogen is a promising clean energy carrier, yet the high energy demand of water electrolysis limits its widespread adoption. Catalysis is crucial to enhance the efficiency of hydrogen production and lower energy costs. However, conventional catalyst design guided by the d-band theory faces inconsistencies in predicting adsorption behavior, and the oxygen evolution reaction (OER) remains a major efficiency bottleneck. To address these challenges, we developed a strain-engineered Rh single-atom catalyst anchored on curved WS2 supported by carbon nanotubes (RhSA/WS2@CNT) to modulate the electronic structure. The resultant catalyst achieves an ultralow overpotential of 17.4 mV at 10 mA cm-2 for the hydrogen evolution reaction (HER) and a mass activity ∼65 times higher than that of commercial Pt/C. Mechanistic analysis reveals that the H* adsorption trend contradicts d-band theory predictions but is explained by orbital symmetry adaptation, where the strain-modulated dxz orbital plays a major role in governing adsorption energetics. Beyond catalyst design, the HER catalyst was coupled with a photocatalytic iodide oxidation reaction (IOR) to replace the OER and reduce the water-splitting voltage to 0.7 V. This study not only introduces a strain-engineering strategy to optimize single-atom catalysts but also demonstrates a coupled electro-photo system that enhances energy efficiency, offering an alternative approach for sustainable hydrogen production.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"6 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594151","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":"Thermal Crystal-to-Crystal Transformation Unlocks Ti8O10(OOC)12-Cluster-Based Metal-Organic Frameworks.","authors":"Lei Gao,Zhenghan Zhang,Jian Li,Shuai Yuan","doi":"10.1021/jacs.5c06825","DOIUrl":"https://doi.org/10.1021/jacs.5c06825","url":null,"abstract":"Titanium-based metal-organic frameworks (Ti-MOFs) are promising photocatalysts, yet their development has been constrained by the limited diversity of Ti-oxo clusters successfully incorporated into MOFs under solvothermal conditions. Herein, we demonstrate a thermal solid-state synthetic strategy to access new Ti-MOFs (MIL-125-HT series) featuring Ti8O10(OOC)12 clusters via the crystal-to-crystal transformation of MIL-125 and its functionalized derivatives. Controlled thermal treatment of MIL-125 induces dehydration and rearrangement of the original Ti8O8(OH)4(OOC)12 clusters while preserving crystallinity and the framework topology. The atomic-resolution structure of MIL-125-HT was determined through three-dimensional electron diffraction and synchrotron powder X-ray diffraction. The phase transition temperature and crystallinity of the resulting MIL-125-HT are governed by the functional groups on the linkers, which affect both the rotational flexibility required for cluster rearrangement and the thermal stability necessary to avoid framework collapse. Naphthalene-based linkers provide an optimal combination of flexibility and robustness, yielding highly crystalline high-temperature phases. Compared to MIL-125, MIL-125-HT exhibits a reduced band gap and enhanced photocatalytic activity in hydrogen peroxide production. This work establishes a solid-state approach for uncovering previously inaccessible Ti-MOFs, broadening their synthetic landscape and enabling new opportunities in photocatalysis.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"10 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594206","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":"Mechanistic Studies of Oxidative Degradation in Diamine-Appended Metal-Organic Frameworks Exhibiting Cooperative CO₂ Capture.","authors":"Shuoyan Xiong, Alistair J Sterling, Nikolay V Tkachenko, Rhea-Donna Reyes, Hsinhan Tsai, Jaeheon Lee, Yu Chen, Yang Wang, Matthew N Dods, David Lu, Ziting Zhu, Jonas Börgel, Jeong Won Kim, Abigail J Schmeiser, Junyang Meng, Hiroyasu Furukawa, Aaron W Peters, Bryan D McCloskey, Jeffrey A Reimer, Simon C Weston, Martin Head-Gordon, Jeffrey R Long","doi":"10.1021/jacs.5c07551","DOIUrl":"https://doi.org/10.1021/jacs.5c07551","url":null,"abstract":"<p><p>Understanding the impact of O₂ during a carbon capture process is vital for designing robust, cost-effective materials for carrying it out. However, mechanistic studies of the O₂-induced degradation of materials are not easily undertaken owing to the complex sequential reaction pathways that arise. Here, we report comprehensive mechanistic investigations of the O₂-induced degradation of diamine-appended metal-organic frameworks (MOFs) exhibiting cooperative CO₂ adsorption. Oxygen exposure experiments were performed on seven different diamine-appended MOFs, including e-2-Mg₂(dobpdc) (e-2 = <i>N</i>-ethylethylenediamine, dobpdc^4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), under various temperatures and O₂ pressures. These experiments show that diamine degradation inhibits CO₂ chemisorption and that the degradation rate is significantly influenced by the diamine structure. In contrast, the parent frameworks remain essentially intact upon O₂ exposure. Detailed characterization of O₂-exposed e-2-Mg₂(dobpdc) revealed the formation of various degradation products, including acetaldehyde, carbon dioxide, water, ethylamine, and other aldehyde- and imine-containing species. Together, these observations suggest that diamine degradation occurs via C-N bond cleavage through pathways involving C-centered radicals. Furthermore, computational evaluation of the initiation and propagation pathways for amine degradation in diamine-appended MOFs indicates that (i) degradation is likely initiated by OH^•, (ii) carbon-centered radicals generated via radical transfer reactions react with O₂, leading to amine degradation, and (iii) the rate-limiting step of the degradation reactions likely involves O-O bond cleavage. Overall, these mechanistic insights could inform strategies for mitigating O₂-induced amine degradation in next-generation carbon capture technologies.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144598929","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":"Probing Strain in Individual Palladium Nanocrystals during Electrochemically Induced Phase Transitions.","authors":"Clément Atlan,Corentin Chatelier,Apinya Ngoipala,Kyle Olson,Arnaud Viola,Ewen Bellec,Michael Grimes,Bruno Gilles,Minaam Qamar,Matous Mrovec,Steven J Leake,Joël Eymery,Tobias U Schülli,Matthias Vandichel,Marie-Ingrid Richard,Frédéric Maillard","doi":"10.1021/jacs.5c05102","DOIUrl":"https://doi.org/10.1021/jacs.5c05102","url":null,"abstract":"The palladium-hydrogen system plays a crucial role in catalysis, hydrogen production and storage, hydrogen embrittlement, and sensing technologies. Understanding the transition of palladium nanocrystals (NCs) from the hydrogen-poor (α) phase to the hydrogen-rich (β) phase is crucial for elucidating hydrogen absorption/desorption mechanisms as well as related phenomena such as hydrogen trapping. In this study, we carefully minimized undesired X-ray beam effects and used in situ Bragg coherent diffraction imaging under electrochemical control to map the strain and lattice parameter distribution within individual palladium NCs across electrochemical potentials relevant to hydrogen absorption and desorption. Lattice parameter changes in both α and β phases are tracked, and reversible strain inversion during the α-to-β phase transition is observed. Through strain and reciprocal space analysis and molecular simulations, a model for the α-to-β phase transition is proposed, which includes a hydrogen-saturated subsurface shell, hydrogen depletion from the α phase during β phase nucleation, and propagation of the β phase in a spherical-cap fashion.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"22 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594150","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":"Competitive Carbonate Binding Hinders Electrochemical CO2 Reduction to CO on Cu Surfaces at Low Overpotentials.","authors":"Jinhui Meng,Jessica Freeze,Linsey Nowack,Chaoyu Li,Hongsen Wang,Héctor D Abruña,Adam P Willard,Victor S Batista,Tianquan Lian","doi":"10.1021/jacs.5c04518","DOIUrl":"https://doi.org/10.1021/jacs.5c04518","url":null,"abstract":"The electrochemical reduction of CO2 to useful chemicals holds promise for a sustainable carbon cycle. However, the key factors that control the pathways to various desired products remain unresolved, partially due to the limited knowledge of reaction intermediates on the electrode surface. To address this, we utilize in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy in combination with density functional theory calculation to examine the potential-dependent composition of adsorbed species during CO2 reduction on polycrystalline copper. The results reveal that carbonate anion adsorption outcompetes other carbon-containing species, including adsorbed CO2 activation intermediate *COO- and *CO, which has the effect of anodically shifting the onset potential of *CO formation in electrolyte solutions with a lower carbonate concentration. These results suggest that the competitive binding of carbonate impedes the reduction of CO2 on the Cu surface. Monte Carlo simulations show that both potential dependent electrode surface change and electrode-carbonate Coulomb interaction are key to understanding the competitive binding process. Our findings suggest that reducing the competitive binding of carbonate may be a promising route to improve the CO2 reduction on Cu electrodes at low overpotentials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"4 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594204","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":"Kinetic Resolution of Heterocyclic Lactams by a Photocatalytic Cobalt-Catalyzed Dehydrogenation.","authors":"Chao Zhou,Thorsten Bach","doi":"10.1021/jacs.5c07524","DOIUrl":"https://doi.org/10.1021/jacs.5c07524","url":null,"abstract":"Chiral heterocyclic lactams have been kinetically resolved in a photochemical process that involves selective hydrogen abstraction by a chiral benzophenone catalyst. Recognition of one enantiomer is achieved by a two-point hydrogen bonding interaction that directs the reactive carbonyl group of the photocatalyst to the C-H bond at the stereogenic center within the lactam. The generated radical is converted to an oxidized product in a cobaloxime-catalyzed dehydrogenation reaction. The unreactive enantiomer is retained and isolated in enantiomerically enriched form (21 examples, 31-56% yield, 90-99% ee).","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594205","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":"Ni-Catalyzed Reductive Ring Contraction via Desulfurative Cross-Coupling.","authors":"Jianhan Zhou,Richard Y Liu","doi":"10.1021/jacs.5c07642","DOIUrl":"https://doi.org/10.1021/jacs.5c07642","url":null,"abstract":"The construction of C-C bonds by contractive \"deletion\" of the sulfur atom from a C-S-C motif is a useful transformation for the synthesis of complex heterocycles. The transformation allows a user to take advantage of the nucleophilic reactivity of sulfur (e.g., for SNAr reactions) and remove that temporary atom at a late stage. A few homogeneous metal systems have been reported to mediate such desulfurizations, but under harsh conditions and, due to the formation of stable oligomeric sulfido complexes, without catalytic turnover. Here, we report a catalytic solution using an accessible Ni precatalyst, inexpensive additives, and mild conditions. The method provides rapid access to a broad scope of fused heterocycles. Preliminary mechanistic studies provide insight into key aspects of the transformation, including the order of C-S bond activations, the synergistic effects of the unusual combination of additives, and the fate of the excised sulfur atom.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"11 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594149","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":"Multistep 11-cis to All-trans Retinal Photoisomerization in Bestrhodopsin, an Unusual Microbial Rhodopsin.","authors":"Matthias Broser,Spyridon Kaziannis,Ivo H M van Stokkum,Atripan Mukherjee,Jakub Dostal,Wayne Busse,Arno Munhoven,Cesar Bernardo,Peter Hegemann,Miroslav Kloz,John T M Kennis","doi":"10.1021/jacs.5c06216","DOIUrl":"https://doi.org/10.1021/jacs.5c06216","url":null,"abstract":"Rhodopsins constitute a broad class of retinal-binding photoreceptors. Microbial rhodopsins are canonically activated through an all-trans to 13-cis photoisomerization, whereas animal rhodopsins are mostly activated through an 11-cis to all-trans isomerization. Bestrhodopsins constitute a special microbial rhodopsin subfamily, with bistable rhodopsin domains that can be photoswitched between a far red-absorbing state D661 and a green-absorbing state P540. Its photochemistry involves a peculiar all-trans to 11-cis isomerization for the D661 to P540 photoreaction and vice versa. Here, we present the P. antarctica bestrhodopsin 11-cis to all-trans photoreaction as determined by femtosecond-to-submillisecond transient absorption, femtosecond stimulated Raman and flash-photolysis spectroscopy. The primary photoreaction involves ultrafast isomerizations in 240 fs from the 11-cis reactant to a mixture of highly distorted all-trans and 13-cis photoproducts. The 13-cis fraction then thermally isomerizes to a distorted all-trans RSB in 120 ps. We propose bicycle pedal models for the branched photoisomerizations with corotation of the C11═C12 and C13═C14 double bonds. One reactant fraction undergoes bicycle pedal motion aborted at the C13═C14 double bond, resulting in all-trans retinal. The other fraction undergoes a full bicycle pedal motion of both C11═C12 and C13═C14, resulting in 13-cis retinal. The primary products are trapped high up the ground-state potential energy surface with a low energetic barrier that facilitates thermal isomerization from 13-cis to all-trans retinal in 120 ps. All-trans retinal then structurally and energetically relaxes with subsequent time constants of 0.7 and 62 μs and 4.4 ms, along with counterion protonation, completing the P540 to D661 photoreaction.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"153 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594203","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":"What Makes Au Nanospheres Superior to Octahedral and Cubic Counterparts for the Deposition of a Pt Monolayer Shell?","authors":"Kei Kwan Li,Lance Kavalsky,Marc Figueras-Valls,Yong Ding,Manos Mavrikakis,Younan Xia","doi":"10.1021/jacs.5c03700","DOIUrl":"https://doi.org/10.1021/jacs.5c03700","url":null,"abstract":"This study demonstrates that Au nanospheres are advantageous over their octahedral and cubic counterparts as seeds in the synthesis of Au@Pt core-shell nanocrystals with a monolayer shell. In combination with experimental characterization, we show through training a machine-learned interatomic potential that the Au nanospheres exhibit a large fraction of low-coordination atoms which are uniformly distributed over the surface. The corresponding high-index facets, including {211}, {311}, {331}, {210}, and {310}, on a spherical seed promote nucleation while greatly shortening the diffusion distance for adatoms. In addition, the high-index facets are instrumental in retaining the deposited Pt atoms on the outermost surface by retarding their inter-diffusional exchange with the underlying Au atoms. By switching from a monolayer made of pure Pt to those made of Pt-Au alloys, we can optimize both the activity and selectivity of the nanocrystals toward the two-electron oxygen reduction reaction for the electrochemical synthesis of H2O2. This method should be extendible to the fabrication of other core-shell nanocatalysts with desired monolayer shells for various catalytic reactions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"47 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594147","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":"Steric Control in Low-Valent Mn Diamide Complexes: Contrasting Magnesium and Manganese in N₂ and Benzene Activation.","authors":"Siad Wolff, Matthew J Evans, Thayalan Rajeshkumar, Dat T Nguyen, Konstantin B Krause, Amanda Opis-Basilio, Christian Herwig, Laurent Maron, Cameron Jones, Christian Limberg","doi":"10.1021/jacs.5c08422","DOIUrl":"https://doi.org/10.1021/jacs.5c08422","url":null,"abstract":"<p><p>Reduction of Mn^II precursors with bulky diamide ligands provided access to a complex with the longest known Mn-Mn bond and to a rare example of N₂ activation at high-spin Mn^I centers. While some instructive parallels can thus be drawn to observations made for Mg analogues, the accessibility of filled d orbitals in the respective Mn^I intermediates leads to a distinct behavior toward benzene that undergoes an oxidative addition.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144598931","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}