Accounts of Chemical Research最新文献

{"title":"Broadband Rotational Spectroscopy in Uniform Supersonic Flows: Chirped Pulse/Uniform Flow for Reaction Dynamics and Low Temperature Kinetics","authors":"Nureshan Dias, Nicolas Suas-David, Shameemah Thawoos, Arthur G. Suits","doi":"10.1021/acs.accounts.4c00489","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00489","url":null,"abstract":"The study of gas-phase chemical reactions at very low temperatures first became possible with the development and implementation of the CRESU (French acronym for Reaction Kinetics in Uniform Supersonic Flows) technique. CRESU relies on a uniform supersonic flow produced by expansion of a gas through a Laval (convergent-divergent) nozzle to produce a wall-less reactor at temperatures from 10 to 200 K and densities of 10¹⁶–10¹⁸ cm^–3 for the study of low temperature kinetics, with particular application to astrochemistry. In recent years, we have combined uniform flows with revolutionary advances in broadband rotational spectroscopy to yield an instrument that affords near-universal detection for novel applications in photodissociation, reaction dynamics, and kinetics. This combination of uniform supersonic flows with chirped-pulse Fourier-transform microwave spectroscopy (Chirped-Pulse/Uniform Flow, CPUF) permits detection of any species with a modest dipole moment, thermalized to the uniform temperature of the gas flow, with isomer, conformer, and vibrational state specificity. In addition, the use of broadband, high-resolution, and time-dependent (microsecond time scale) micro- and mm-wave spectroscopy makes it an ideal tool for characterizing both transient and stable molecules, as well as studying their spectroscopy and dynamics.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439474","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":"Conversion of Carbon Dioxide into Molecular-based Porous Frameworks","authors":"Kentaro Kadota, Satoshi Horike","doi":"10.1021/acs.accounts.4c00519","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00519","url":null,"abstract":"The conversion of carbon dioxide (CO₂) to value-added functional materials is a major challenge in realizing a carbon-neutral society. Although CO₂ is an attractive renewable carbon resource with high natural abundance, its chemical inertness has made the conversion of CO₂ into materials with the desired structures and functionality difficult. Molecular-based porous materials, such as metal–organic frameworks (MOFs) and covalent–organic frameworks (COFs), are designable porous solids constructed from molecular-based building units. While MOF/COFs attract wide attention as functional porous materials, the synthetic methods to convert CO₂ into MOF/COFs have been unexplored due to the lack of synthetic guidelines for converting CO₂ into molecular-based building units.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431765","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":"Mechanisms of Controllable Growth and Ohmic Contact of Two-Dimensional Molybdenum Disulfide: Insight from Atomistic Simulations","authors":"Liang Ma, Xiaoshu Gong, Ruikang Dong, Jinlan Wang","doi":"10.1021/acs.accounts.4c00495","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00495","url":null,"abstract":"Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs), in particular molybdenum disulfide (MoS₂), have recently attracted huge interest due to their proper bandgap, high mobility at 2D limit, and easy-to-integrate planar structure, which are very promising for extending Moore’s law in postsilicon electronics technology. Great effort has been devoted toward such a goal since the demonstration of protype MoS₂ devices with high room-temperature on/off current ratios, ultralow standby power consumption, and atomic level scaling capacity down to sub-1-nm technology node. However, there are still several key challenges that need to be addressed prior to the real application of MoS₂-based electronics technology. The controllable growth of wafer-scale single-crystal MoS₂ on industry-compatible insulating substrates is the prerequisite of application while the currently synthesized MoS₂ films mostly are polycrystalline with limited sizes of single-crystal domains and may involve metal substrates. The precise layer-control is also very important for MoS₂ growth since its electronic properties are layer-dependent, whereas the layer-by-layer growth of multilayer MoS₂ dominated by the van der Waals (vdW) epitaxy leads to poor thickness uniformity and noncontinuously distributed domains. High density up to 10¹³ cm^–2 of sulfur vacancies (SVs) in grown MoS₂ can cause unfavorable carrier scatting and electronic properties variations and will inevitably disturb the device performance. The dangling-bond-free surface of MoS₂ gives rise to an inherent vdW gap at metal–semiconductor (M–S) contact, which leads to high electrical resistance and poor current-delivery capability at the contact interface and thereby substantially limits the performances of MoS₂ devices.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405661","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":"MOF-on-MOF Growth: Inducing Naturally Nonpreferred MOFs and Atypical MOF Growth","authors":"Sujeong Lee, Gihyun Lee, Moonhyun Oh","doi":"10.1021/acs.accounts.4c00469","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00469","url":null,"abstract":"Overflowing metal–organic frameworks (MOFs) have been synthesized from a wide range of metal and organic components for specific purposes and intellectual curiosity. Each MOF has unique chemical and structural characteristics directed by the incorporated components, metal ions (or clusters), organic linkers, and their intrinsic coordination interactions. These incorporated components and structural characteristics are two pivotal factors influencing MOFs’ fundamental properties and subsequent applications. Therefore, selecting the appropriate metal and organic components, considering their innate chemical and structural properties, is crucial to endow the final MOFs with the desired properties. Ultimately, producing MOFs with a desired structure using ideal components is the best approach to achieving the best MOFs tailored for specific purposes with desired properties. However, achieving MOFs with the intended structure from chosen components remains underdeveloped. In many cases, the resulting MOF structure is governed by the thermodynamically and/or kinetically preferred configuration (refers to a naturally preferred structure) of the chosen components and given reaction conditions. Additionally, producing hybrid MOFs with complex components, structures, and morphologies presents a great opportunity to obtain special MOFs with advanced properties and functions. In this Account, we outline our group’s efforts over the past few years to develop naturally nonpreferred MOFs through the induced MOF-on-MOF growth process and atypical hybrid MOFs via nonstandard MOF-on-MOF growth. First, we highlight the prime strategy for producing naturally nonpreferred MOFs based on template-induced MOF-on-MOF growth. In this section, we discuss the two basic growth behaviors, isotropic and anisotropic growth of naturally nonpreferred MOFs, determined by the degree of matching between the cell lattices of the two MOFs. Second, we introduce the MOF farming concept for the productive cultivation and effective harvesting of naturally nonpreferred MOFs made by MOF-on-MOF growth. Here we discuss the importance of selecting the ideal MOF template for productive growth and developing an efficient method for harvesting cultivated MOFs. Next, we describe atypical anisotropic MOF-on-MOF growths between two MOFs with mismatched cell lattices. In this section, we introduce tip-to-middle MOF-on-MOF growth involving self-structural adjustment of the secondary MOF, logical inference of unidentified MOF structures based on MOF-on-MOF growth behavior and morphological features, and MOF-on-MOF growth accompanied by etching and transformation of the template. Finally, we discuss the perspectives and challenges of MOF-on-MOF growth and the synthesis of naturally nonpreferred MOFs. We hope that this Account offers valuable insights into the rational design and development of MOFs with desired structural and compositional characteristics, leading to the creation of ideal MOFs.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398404","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":"Hierarchical Equations of Motion for Quantum Chemical Dynamics: Recent Methodology Developments and Applications","authors":"Shuming Bai, Shuocang Zhang, Chenghong Huang, Qiang Shi","doi":"10.1021/acs.accounts.4c00492","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00492","url":null,"abstract":"Quantum effects are critical to understanding many chemical dynamical processes in condensed phases, where interactions between molecules and their environment are usually strong and non-Markovian. In this Account, we review recent progress from our group in development and application of the hierarchical equations of motion (HEOM) method, highlighting its ability to address some challenging problems in quantum chemical dynamics.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385568","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":"Activating Metal–Organic Cages by Incorporating Functional M(ImPhen)3 Metalloligands: From Structural Design to Applications","authors":"Yu-Lin Lu, Ya-Ping Wang, Kai Wu, Mei Pan, Cheng-Yong Su","doi":"10.1021/acs.accounts.4c00467","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00467","url":null,"abstract":"The emulation of ingenious biofunctions has been a research focus for several decades. Metal–organic cages (MOCs), as a type of discrete supramolecular assembly with well-defined shapes and cavities, have aroused great interest in chemists to imitate natural protein cages or enzymes. However, to genuinely achieve tailored functionalities or reactivities of enzymes, the design of cage structures combining both the confined microenvironment and the active site is a prerequisite. Therefore, the integration of functionalized motifs into MOCs is expected to provide a feasible approach to construct biofunctional confined nanospaces, which not only allows the modulation of cage properties for applications such as molecular recognition, transport, and catalysis but also creates unique microenvironments that promote enzymatic effects for special reactivities and selectivities, thereby providing a versatile platform to achieve exceptional biomimetic functions and beyond.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142385998","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 Science and Engineering for Electrochemical Materials","authors":"Zhiming Liang, Mohammad Sufiyan Nafis, Dakota Rodriguez, Chunmei Ban","doi":"10.1021/acs.accounts.4c00433","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00433","url":null,"abstract":"In electrochemical energy storage systems, the reversible storage capacity of battery materials often degrades due to parasitic reactions at the electrode–electrolyte interface, transitional metal dissolution, and metallic dendrite growth at the surface. Surface engineering techniques offer the opportunity to modify the composition and structure of a surface, thereby enabling control over chemical reactions occurring at the surface and manipulating chemical interactions at the solid–solid or solid–liquid interface. These modifications can help stabilize the surface of electrode materials and prevent unwanted reactions with electrolytes without changing the original properties of the bulk structure. This allows for achieving full theoretical capacity and maximizing battery material capacity retention with minimal overpotentials. In the past decade, our teams have been working on developing a variety of surface engineering techniques. These include applying atomic and molecular layer deposition (ALD and MLD), templating, doping, and coating via wet-chemical processes to stabilize the surfaces of electrode materials. The aim is to mitigate parasitic side-reactions without impeding charge transfer kinetics, suppress dendrite growth, and ultimately improve the electrode performance.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142384942","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":"From Catalysis of Evolution to Evolution of Catalysis.","authors":"Rotem Edri, Loren Dean Williams, Moran Frenkel-Pinter","doi":"10.1021/acs.accounts.4c00196","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00196","url":null,"abstract":"<p><p>ConspectusThe mystery of the origins of life is one of the most difficult yet intriguing challenges to which humanity has grappled. How did biopolymers emerge in the absence of enzymes (evolved biocatalysts), and how did long-lasting chemical evolution find a path to the highly selective complex biology that we observe today? In this paper, we discuss a chemical framework that explores the very roots of catalysis, demonstrating how standard catalytic activity based on chemical and physical principles can evolve into complex machineries. We provide several examples of how prebiotic catalysis by small molecules can be exploited to facilitate polymerization, which in biology has transformed the nature of catalysis. Thus, catalysis evolved, and evolution was catalyzed, during the transformation of prebiotic chemistry to biochemistry. Traditionally, a catalyst is defined as a substance that (i) speeds up a chemical reaction by lowering activation energy through different chemical mechanisms and (ii) is not consumed during the course of the reaction. However, considering prebiotic chemistry, which involved a highly diverse chemical space (i.e., high number of potential reactants and products) and constantly changing environment that lacked highly sophisticated catalytic machinery, we stress here that a more primitive, broader definition should be considered. Here, we consider a catalyst as any chemical species that lowers activation energy. We further discuss various demonstrations of how simple prebiotic molecules such as hydroxy acids and mercaptoacids promote the formation of peptide bonds via energetically favored exchange reactions. Even though the small molecules are partially regenerated and partially retained within the resulting oligomers, these prebiotic catalysts fulfill their primary role. Catalysis by metal ions and in complex chemical mixtures is also highlighted. We underline how chemical evolution is primarily dictated by kinetics rather than thermodynamics and demonstrate a novel concept to support this notion. Moreover, we propose a new perspective on the role of water in prebiotic catalysis. The role of water as simply a \"medium\" obscures its importance as an active participant in the chemistry of life, specifically as a very efficient catalyst and as a participant in many chemical transformations. Here we highlight the unusual contribution of water to increasing complexification over the course of chemical evolution. We discuss possible pathways by which prebiotic catalysis promoted chemical selection and complexification. Taken together, this Account draws a connection line between prebiotic catalysis and contemporary biocatalysis and demonstrates that the fundamental elements of chemical catalysis are embedded within today's biocatalysts. This Account illustrates how the evolution of catalysis was intertwined with chemical evolution from the very beginning.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379420","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":"Porous Metal Phosphonate Frameworks: Construction and Physical Properties.","authors":"Tao Zheng, Wenzhuo Tan, Li-Min Zheng","doi":"10.1021/acs.accounts.4c00337","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00337","url":null,"abstract":"&lt;p&gt;&lt;p&gt;ConspectusPorous metal phosphonate frameworks (PMPFs) as a subclass of metal-organic frameworks (MOFs) have promising applications in the fields of gas adsorption and separation, ion exchange and storage, catalysis, sensing, etc. Compared to the typical carboxylate-based MOFs, PMPFs exhibit higher thermal and water stability due to the strong coordination ability of the phosphonate ligands. Despite their robust frameworks, PMPFs account for less than 0.51% of the porous MOFs reported so far. This is because metal phosphonates are highly susceptible to the formation of dense layered or pillared-layered structures, and they precipitate easily and are difficult to crystallize. There is a tendency to use phosphonate ligands containing multiple phosphonate groups and large organic spacers to prevent the formation of dense structures and generate open frameworks with permanent porosity. Thus, many PMPFs are composed of chains or clusters of inorganic metal phosphonates interconnected by organic spacers. Using this feature, a wide range of metal ions and organic components can be selected, and their physical properties can be modulated. However, limited by the small number of PMPFs, there are still relatively few studies on the physical properties of PMPFs, some of which merely remain in the description of the phenomena and lack in-depth elaboration of the structure-property relationship. In this Account, we review the strategies for constructing PMPFs and their physical properties, primarily based on our own research. The construction strategies are categorized according to the number (&lt;i&gt;n&lt;/i&gt; = 1-4) of phosphonate groups in the ligand. The physical properties include proton conduction, electrical conduction, magnetism, and photoluminescence properties. Proton conductivity of PMPFs can be enhanced by increasing the proton carrier concentration and mobility. The former can be achieved by adding acidic groups such as -POH and/or introducing acidic guests in the hydrophilic channels. The latter can be attained by introducing conjugate acid-base pairs or elevating the temperature. Semiconducting PMPFs, on the other hand, can be obtained by constructing highly conjugated networks of coordination bonds or introducing large conjugated organic linkers π-π stacked in the lattice. In the case of magnetic PMPFs, long-range magnetic ordering occurs at very low temperatures due to very weak magnetic exchange couplings propagated via O-P-O and/or O(P) units. However, lanthanide compounds may be interesting candidates for single-molecule magnets because of the strong single-ion magnetic anisotropy arising from the spin-orbit coupling and large magnetic moments of lanthanide ions. The luminescent properties of PMPFs depend on the metal ions and/or organic ligands. Emissive PMPFs containing lanthanides and/or uranyl ions are promising for sensing and photonic applications. We conclude with an outlook on the opportunities and challenges for the future development","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379418","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":"Superlattice Assembly for Empowering Metal Nanoclusters","authors":"Hao Li, Xi Kang, Manzhou Zhu","doi":"10.1021/acs.accounts.4c00521","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00521","url":null,"abstract":"Atomically precise metal nanoclusters, serving as an aggregation state of metal atoms, display unique physicochemical properties owing to their ultrasmall sizes with discrete electronic energy levels and strong quantum size effects. Such intriguing properties endow nanoclusters with potential utilization as efficient nanomaterials in catalysis, electron transfer, drug delivery, photothermal conversion, optical control, etc. With the assistance of atomically precise operations and theoretical calculations on metal nanoclusters, significant progress has been accomplished in illustrating their structure–performance correlations at the single-molecule level. Such research achievements, in turn, have contributed to the rational design and customization of functional nanoclusters and cluster-based nanomaterials.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142384107","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}