Journal of the American Chemical Society最新文献

Solid-State Electrochemical Carbon Dioxide Capture by Conductive Metal-Organic Framework Incorporating Nickel Bis(diimine) Units. 含有双(二亚胺)镍单元的导电金属有机框架的固态电化学二氧化碳捕获。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-19 DOI: 10.1021/jacs.4c10654

Jinxin Liu, Mingyu Yang, Xinyi Zhou, Zheng Meng

{"title":"Solid-State Electrochemical Carbon Dioxide Capture by Conductive Metal-Organic Framework Incorporating Nickel Bis(diimine) Units.","authors":"Jinxin Liu, Mingyu Yang, Xinyi Zhou, Zheng Meng","doi":"10.1021/jacs.4c10654","DOIUrl":"https://doi.org/10.1021/jacs.4c10654","url":null,"abstract":"This paper presents the first implementation of electrically conductive metal-organic framework (MOF) Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 (Ni3(HITP)2) integrated with nickel bis(diimine) (Ni-BDI) units for efficient solid-state electrochemical carbon dioxide (CO2) capture. The electrochemical cell assembled using Ni3(HITP)2 as working electrodes can reversibly capture and release CO2 through potential control. A high-capacity utilization of 96% and a Faraday efficiency of 98% have been achieved. The material also exhibits excellent electrochemical stability with its capacity maintained during 50 capture-release cycles and resistance to general interferences, including O2, H2O, NO2, and SO2. Capacity utilization of up to 35% is obtained at CO2 concentrations as low as 1%. The capture of CO2 at concentrations ranging from 1% to 100% requires exceptionally low energy consumption of only 30.5-72.4 kJ mol-1. Studies combining spectroscopic experiments and computational approaches reveal that the CO2 capture and release mechanism involves reversible carbamate formation on the N atom of the Ni-BDI unit in the MOF upon its one-electron redox reaction.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666312","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}

引用次数: 0

Smallest [5,6]Fullerene as Building Blocks for 2D Networks with Superior Stability and Enhanced Photocatalytic Performance. 将最小的 [5,6]Fullerene 作为具有卓越稳定性和增强光催化性能的二维网络的基石。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-19 DOI: 10.1021/jacs.4c13167

Jiaqi Wu, Bo Peng

{"title":"Smallest [5,6]Fullerene as Building Blocks for 2D Networks with Superior Stability and Enhanced Photocatalytic Performance.","authors":"Jiaqi Wu, Bo Peng","doi":"10.1021/jacs.4c13167","DOIUrl":"https://doi.org/10.1021/jacs.4c13167","url":null,"abstract":"The assembly of molecules to form covalent networks can create varied lattice structures with physical and chemical properties distinct from those of conventional atomic lattices. Using the smallest stable [5,6]fullerene units as building blocks, various 2D C24 networks can be formed with superior stability and strength compared to the recently synthesized monolayer polymeric C60. Monolayer C24 harnesses the properties of both carbon crystals and fullerene molecules, such as stable chemical bonds, suitable band gaps, and large surface area, facilitating photocatalytic water splitting. The electronic band gaps of C24 are comparable to those of TiO2, providing appropriate band edges with sufficient external potential for overall water splitting over the acidic and neutral pH range. Upon photoexcitation, strong solar absorption enabled by strongly bound bright excitons can generate carriers effectively, while the type-II band alignment between C24 and other 2D monolayers can separate electrons and holes in individual layers simultaneously. Additionally, the number of surface-active sites of C24 monolayers are three times more than that of their C60 counterparts in a much wider pH range, providing spontaneous reaction pathways for the hydrogen evolution reaction. Our work provides insights into materials design using tunable building blocks of fullerene units with tailored functions for energy generation, conversion, and storage.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666278","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}

引用次数: 0

Interzeolite Transformation through Cross-Nucleation: A Molecular Mechanism for Seed-Assisted Synthesis. 通过交叉成核实现互斑岩转化：种子辅助合成的分子机制。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-19 DOI: 10.1021/jacs.4c12863

Carlos Chu-Jon, Eli Martinez, Andressa A Bertolazzo, Suvo Banik, Jeffrey D Rimer, Subramanian K R S Sankaranarayanan, Valeria Molinero

{"title":"Interzeolite Transformation through Cross-Nucleation: A Molecular Mechanism for Seed-Assisted Synthesis.","authors":"Carlos Chu-Jon, Eli Martinez, Andressa A Bertolazzo, Suvo Banik, Jeffrey D Rimer, Subramanian K R S Sankaranarayanan, Valeria Molinero","doi":"10.1021/jacs.4c12863","DOIUrl":"https://doi.org/10.1021/jacs.4c12863","url":null,"abstract":"Polymorph selection and efficient crystallization are central goals in zeolite synthesis. Crystalline seeds are used for both purposes. While it has been proposed that zeolite seeds induce interzeolite transformation by dissolving into structural units that promote nucleation of the daughter crystal, the seed's structural elements do not always match those of the target zeolite. This discrepancy raises the question of how the seed promotes the daughter phase. Here, we present the first molecularly resolved investigation of seed-assisted zeolite synthesis. Using molecular simulations, we reproduce the experimental finding that a parent zeolite can promote the nucleation of a daughter zeolite even when it lacks common composite building units (CBUs) or crystal planes. Modeling the seed-assisted synthesis of an AFI-type zeolite using zeolite CHA, our simulations indicate that stand-alone CBUs from the parent seed do not facilitate daughter crystal formation. However, introducing the intact seed significantly reduces the synthesis time, supporting that seed integrity is key to increased efficiency. This reduction arises from the cross-nucleation of the AFI-type zeolite on the CHA (001) face. We find that parent and daughter zeolites are connected by an interfacial transition layer with an order distinct from that of both zeolites. Simulations reveal that cross-nucleation occurs over a broad range of synthesis conditions. We argue that cross-nucleation would be most favorable for zeolite pairs that share crystalline planes such as those forming intergrowths. Our findings suggest that the prevalence of intergrowths with a common lattice plane in zeolite synthesis is likely a kinetic effect of accelerated cross-nucleation.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666186","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}

引用次数: 0

Template and Solid-State-Assisted Assembly of an M₉L₆ Expanded Coordination Cage for Medium-Sized Molecule Encapsulation. 用于中等尺寸分子封装的 M9L6 扩展配位笼的模板和固态辅助组装。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-18 DOI: 10.1021/jacs.4c14509

Kenta Iizuka, Hiroki Takezawa, Makoto Fujita

引用次数: 0

Photons, Excitons, and Electrons in Covalent Organic Frameworks. 共价有机框架中的光子、激子和电子。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-18 DOI: 10.1021/jacs.3c14833

Dominic Blätte, Frank Ortmann, Thomas Bein

{"title":"Photons, Excitons, and Electrons in Covalent Organic Frameworks.","authors":"Dominic Blätte, Frank Ortmann, Thomas Bein","doi":"10.1021/jacs.3c14833","DOIUrl":"https://doi.org/10.1021/jacs.3c14833","url":null,"abstract":"Covalent organic frameworks (COFs) are created by the condensation of molecular building blocks and nodes to form two-dimensional (2D) or three-dimensional (3D) crystalline frameworks. The diversity of molecular building blocks with different properties and functionalities and the large number of possible framework topologies open a vast space of possible well-defined porous architectures. Besides more classical applications of porous materials such as molecular absorption, separation, and catalytic conversions, interest in the optoelectronic properties of COFs has recently increased considerably. The electronic properties of both the molecular building blocks and their linkage chemistry can be controlled to tune photon absorption and emission, to create excitons and charge carriers, and to use these charge carriers in different applications such as photocatalysis, luminescence, chemical sensing, and photovoltaics. In this Perspective, we will discuss the relationship between the structural features of COFs and their optoelectronic properties, starting with the building blocks and their chemical connectivity, layer stacking in 2D COFs, control over defects and morphology including thin film synthesis, exploring the theoretical modeling of structural, electronic, and dynamic features of COFs, and discussing recent intriguing applications with a focus on photocatalysis and photoelectrochemistry. We conclude with some remarks about present challenges and future prospects of this powerful architectural paradigm.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666192","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}

引用次数: 0

Specific Adsorption of Alkaline Cations Enhances CO-CO Coupling in CO₂ Electroreduction. 碱性阳离子的特定吸附增强了二氧化碳电还原中的 CO-CO 偶联。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-18 DOI: 10.1021/jacs.4c10455

Yanyang Qin, Chenfeng Xia, Tiantian Wu, Jianrui Zhang, Guoxin Gao, Bao Yu Xia, Michelle L Coote, Shujiang Ding, Yaqiong Su

{"title":"Specific Adsorption of Alkaline Cations Enhances CO-CO Coupling in CO2 Electroreduction.","authors":"Yanyang Qin, Chenfeng Xia, Tiantian Wu, Jianrui Zhang, Guoxin Gao, Bao Yu Xia, Michelle L Coote, Shujiang Ding, Yaqiong Su","doi":"10.1021/jacs.4c10455","DOIUrl":"https://doi.org/10.1021/jacs.4c10455","url":null,"abstract":"Electrolyte alkaline cations can significantly modulate the reaction selectivity of electrochemical CO2 reduction (eCO2R), enhancing the yield of the valuable multicarbon (C2+) chemical feedstocks. However, the mechanism underlying this cation effect on the C-C coupling remains unclear. Herein, by performing constant-potential AIMD simulations, we studied the dynamic behavior of interfacial K+ ions over Cu surfaces during C-C coupling and the origin of the cation effect. We showed that the specific adsorption of K+ readily occurs at the surface sites adjacent to the *CO intermediates on the Cu surfaces. Furthermore, this specific adsorption of K+ during *CO-*CO coupling is more important than quasi-specific adsorption for enhancing coupling kinetics, reducing the coupling barriers by approximately 0.20 eV. Electronic structure analysis revealed that charge redistribution occurs between the specifically adsorbed K+, *CO, and Cu sites, and this can account for the reduced barriers. In addition, we identified excellent *CO-*CO coupling selectivity on Cu(100) with K+ ions. Experimental results show that suppressing surface K+-specific adsorption using the surfactant cetyltrimethylammonium bromide (CTAB) significantly decreases the Faradaic efficiency for C2 products from 41.1% to 4.3%, consistent with our computational findings. This study provides crucial insights for improving the selectivity toward C2+ products by rationally tuning interfacial cation adsorption during eCO2R. Specifically, C-C coupling can be enhanced by promoting K+-specific adsorption, for example, by confining K+ within a coated layer or using pulsed negative potentials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666331","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}

引用次数: 0

Retraction of "Bisboronic Acids for Selective, Physiologically Relevant Direct Glucose Sensing with Surface-Enhanced Raman Spectroscopy". 撤回 "利用表面增强拉曼光谱对双硼酸进行选择性、生理学相关的直接葡萄糖传感 "一文。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-18 DOI: 10.1021/jacs.4c11001

Bhavya Sharma, Pradeep Bugga, Lindsey R Madison, Anne-Isabelle Henry, Martin G Blaber, Nathan G Greeneltch, Naihao Chiang, Milan Mrksich, George C Schatz, Richard P Van Duyne

引用次数: 0

Photocyclization of Fluorinated Acetophenones Unlocks an Efficient Way to Solar Energy Storage. 氟化苯乙酮的光环化为太阳能储存开辟了一条有效途径。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-18 DOI: 10.1021/jacs.4c12249

Henning Maag, Matthias Schmitz, Alexander Sandvoß, Domenik Mundil, Abhilash Pedada, Felix Glaser, Christoph Kerzig, Johannes M Wahl

{"title":"Photocyclization of Fluorinated Acetophenones Unlocks an Efficient Way to Solar Energy Storage.","authors":"Henning Maag, Matthias Schmitz, Alexander Sandvoß, Domenik Mundil, Abhilash Pedada, Felix Glaser, Christoph Kerzig, Johannes M Wahl","doi":"10.1021/jacs.4c12249","DOIUrl":"https://doi.org/10.1021/jacs.4c12249","url":null,"abstract":"The ability to store and release energy efficiently is crucial for advancing sustainable energy technologies, and light-driven molecular isomerization presents a promising solution. However, a persistent challenge in this field is achieving both high stability of the energy-storing photoisomer and establishing efficient catalysis for back-isomerization, a critical process for releasing the stored energy as heat. In this work, we introduce a conceptually new molecular system designed for long-term energy storage, which is based on the reversible isomerization of ortho-methylacetophenone ⇄ benzocyclobutenol. Key to the success of this system is the strategic placement of a trifluoromethyl group, which enhances the overall performance by preventing unwanted side reactions during photochemical cyclization and by increasing the stability of the benzocyclobutenol moiety. Back isomerization is established using simple organic bases as catalysts, taking advantage of significant rate differences between normal and anionic electrocyclic ring-openings. This approach allows for controlled and predictable heat release under ambient conditions, positioning this molecular pair as a promising candidate for practical energy storage solutions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666190","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}

引用次数: 0

Thermally Stable Capacitive Energy-Density and Colossal Electrocaloric and Pyroelectric Effects of Sm-Doped Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ Thin Films. 掺杂 Sm 的 Pb（Mg1/3Nb2/3）O3-PbTiO3 薄膜的热稳定电容能量密度以及巨大的电致发光和热释电效应。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-18 DOI: 10.1021/jacs.4c11555

Zouhair Hanani, Jamal Belhadi, Urška Trstenjak, Nick A Shepelin, Vid Bobnar, Hana Uršič, Nina Daneu, Nikola Novak, David Fabijan, Anna Razumnaya, Yuri Tikhonov, Thomas Lippert, Zdravko Kutnjak, Gertjan Koster, Igor Lukyanchuk, Matjaž Spreitzer

{"title":"Thermally Stable Capacitive Energy-Density and Colossal Electrocaloric and Pyroelectric Effects of Sm-Doped Pb(Mg1/3Nb2/3)O3-PbTiO3 Thin Films.","authors":"Zouhair Hanani, Jamal Belhadi, Urška Trstenjak, Nick A Shepelin, Vid Bobnar, Hana Uršič, Nina Daneu, Nikola Novak, David Fabijan, Anna Razumnaya, Yuri Tikhonov, Thomas Lippert, Zdravko Kutnjak, Gertjan Koster, Igor Lukyanchuk, Matjaž Spreitzer","doi":"10.1021/jacs.4c11555","DOIUrl":"https://doi.org/10.1021/jacs.4c11555","url":null,"abstract":"Sm-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (Sm-PMN-PT) bulk materials have revealed outstanding ferroelectric and piezoelectric properties due to enhanced local structural heterogeneity. In this study, we further explore the potential of Sm-PMN-PT by fabricating epitaxial thin films by pulsed laser deposition, revealing that Sm doping significantly improves the capacitive energy-storage, piezoelectric, electrocaloric, and pyroelectric properties of PMN-PT thin films. These Sm-PMN-PT thin films exhibit fatigue-free performance up to 109 charge-discharge cycles and maintain thermal stability across a wide temperature range from -40 to 200 °C. Notably, the films demonstrate a colossal electrocaloric effect with a temperature change of 59.4 K and a remarkable pyroelectric energy density reaching 40 J cm-3. By using scanning transmission electron microscopy and phase-field modeling, we revealed that these exceptional properties arise from the increased local structural heterogeneity and strong local electric fields along spontaneous polarization directions, facilitating the nucleation of polymorphic nanodomains characterized by a slush-like polar structure. These findings highlight the enormous potential of Sm-PMN-PT films in capacitive energy storage and solid-state electrothermal energy interconversion. Furthermore, this approach holds broad potential for other relaxor ferroelectrics by enabling the manipulation of nanodomain structures, paving the way for developing robust multifunctional materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666305","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}

引用次数: 0

Unwinding Spherical Helices Increases Entropy and Stability of Frank-Kasper and Body-Centered-Cubic Periodic Arrays To Facilitate Discrimination between Self-Organization Mechanisms. 释放球形螺旋会增加弗兰克-卡斯帕和体心立方周期阵列的熵和稳定性，从而促进自组织机制之间的区别。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-11-18 DOI: 10.1021/jacs.4c13688

Dipankar Sahoo, Mihai Peterca, Virgil Percec

{"title":"Unwinding Spherical Helices Increases Entropy and Stability of Frank-Kasper and Body-Centered-Cubic Periodic Arrays To Facilitate Discrimination between Self-Organization Mechanisms.","authors":"Dipankar Sahoo, Mihai Peterca, Virgil Percec","doi":"10.1021/jacs.4c13688","DOIUrl":"https://doi.org/10.1021/jacs.4c13688","url":null,"abstract":"Spherical supramolecular dendrimers including helical, self-organize soft Frank-Kasper, other cubic such as body-centered cubic, and quasicrystal periodic and quasiperiodic arrays. When any of these periodic or quasiperiodic arrays forms immediately above a columnar phase, a supramolecular orientational memory effect was found to discriminate between mechanisms of self-organization of supramolecular spheres and generate unprecedented periodic arrays of helical columns which cannot be constructed by any other methodology. Here, we demonstrate that unwinding spherical helices, via their precursor nonhelical columns, increases the entropy and stability of their periodic and quasiperiodic spherical arrays and places the Frank-Kasper and other cubic phases immediately above the columnar phase. This process is not available in biology where spherical viruses self-organize body-centered cubic lattices. However, this concept reengineers, on increasing temperature, the originally expected position of the periodic and quasiperiodic array versus that of the columnar lattice. This process facilitates discrimination between different self-organization mechanisms of supramolecular spheres and also mediates the emergence of unprecedentedly complex and technologically important periodic arrays of nonhelical columns.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":14.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142666319","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}

引用次数: 0