Accounts of Chemical Research最新文献

{"title":"Dirhodium-Catalyzed Asymmetric Transformations of Alkynes via Carbene Intermediates.","authors":"Rui Wu, Zurong Xu, Dong Zhu, Shifa Zhu","doi":"10.1021/acs.accounts.4c00715","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00715","url":null,"abstract":"<p><p>ConspectusFunctionalization of alkynes is an established cornerstone of organic synthesis. While numerous transition metals exhibit promising activities in the transformations of alkynes via π-insertion or oxidative cyclometalation, Lewis π-acids offer a different approach. By coordinating with alkynes through π-bonding, Lewis π-acids facilitate nucleophilic addition, leading to the formation of alkenyl metal species. These species can undergo electron rearrangement to generate metal carbenes, which are crucial intermediates for subsequent carbene transfer reactions. This reaction pathway provides a versatile route for alkyne functionalization, especially in an asymmetric manner. Although the Lewis π-acid, gold(I), pioneered this reaction mode, the development of asymmetric variants remains challenging due to the linear coordination of gold(I). Therefore, expanding the range of catalysts beyond gold(I) complexes to other metal catalysts would facilitate further advances in chiral molecule construction and the exploration of novel reaction modes.In this Account, we present a concise review of alkyne multifunctionalization via dirhodium-catalyzed asymmetric transformations, providing the development of the modulation strategies and substrates and plausible reaction mechanisms. In the aromatization-driven strategy, the furanyl dirhodium carbene is generated from an enynone, which is terminated by enantioselective intramolecular C-H insertion, cyclopropanation, aromatic substitution, or the Büchner reaction, giving chiral dihydroindoles, dihydrobenzofurans, cyclopropane-fused tetrahydroquinolines, fluorenes, or cyclohepta[<i>b</i>]benzofurans. The cap-tether modulation strategy was developed in a subsequent study to balance the reactivity and selectivity of an azo-enyne. This strategy gave the first catalytic asymmetric cycloisomerization of azo-enyne, affording centrally and axially chiral isoindazole derivatives. The synergistic activation strategy, i.e., EWG activation and C-H···O interaction, was introduced to achieve the first dirhodium-catalyzed asymmetric cycloisomerization of enynes, providing a range of chiral cyclopropane-annulated bicyclic systems from enynals. Benefiting from these successes, difluoromethyl-substituted enynes were designed and proven to be effective substrates. With the corresponding benzo-1,6-enynes as the substrates, the enantioselective biscyclopropanation and the cascaded cyclopropanation/cyclopropenation were achieved using alkynes as dicarbene equivalents. Additionally, benzo-1,5-enynal generated vinyl dirhodium carbene, which reacted with a variety of alkenes via [2 + 1] cycloaddition, [4 + 3] cycloaddition, or formal allylation, giving spiro and fused polycyclic heterocycles. Coupling the synergistic activation strategy with desymmetrization, we further successfully achieved the asymmetric cycloisomerization of diynals, constructing furan-fused dihydropiperidines with an alkyne-substituted aza-quaternary ste","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":" ","pages":""},"PeriodicalIF":16.4,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062100","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":"Strategies and Prospects for Engineering a Stable Zn Metal Battery: Cathode, Anode, and Electrolyte Perspectives","authors":"Kang Zhou, Xiaomeng Yu, Xiaoli Dong*, Ziyang Guo* and Yonggang Wang*, ","doi":"10.1021/acs.accounts.4c0077610.1021/acs.accounts.4c00776","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00776https://doi.org/10.1021/acs.accounts.4c00776","url":null,"abstract":"<p >Zinc metal batteries (ZMBs) appear to be promising candidates to replace lithium-ion batteries owing to their higher safety and lower cost. Moreover, natural reserves of Zn are abundant, being approximately 300 times greater than those of Li. However, there are some typical issues impeding the wide application of ZMBs. Traditional inorganic cathodes exhibit an unsatisfactory cycling lifetime because of structure collapse and active materials dissolution. Apart from inorganic cathodes, organic materials are now gaining extensive attention as ZMBs cathodes because of their sustainability, high environmental friendliness, and tunable molecule structure which make them usually exhibit superior cycling life. Nevertheless, due to the inferior conductivity of organic materials, their mass loading and volumetric energy density still cannot meet our demands. In addition, the specific working mechanism of inorganic/organic cathodes also needs further investigation, necessitating the use of advanced in situ characterization technologies. Reversibility of metallic Zn anodes is also crucial in determining the overall cell performances. Like Li and Na anodes, uncontrolled dendrite growth is also an annoying problem for Zn anodes, which may penetrate the separator and cause inner short circuit. In aqueous electrolyte, highly reactive H<sub>2</sub>O molecules easily attack metallic Zn anode, leading to undesired Zn corrosion. Furthermore, during cell operation, hydrogen evolution reaction (HER) occurs, which leads to continuous consumption of electrolytes and formation of insulating byproducts on Zn anodes. Although strategies like novel Zn anode design and artificial SEI layer construction are proposed to inhibit dendrites growth and protect Zn anodes from active H<sub>2</sub>O attack, the corresponding manufacturing process remains complex. Modifying electrolyte components is relatively simple to implement and effectively stabilizes Zn anodes. However, HER cannot be completely eliminated when H<sub>2</sub>O exists in the modified electrolytes. Under such conditions, nonaqueous electrolytes appear to be a promising solution for ZMBs in the future due to their aprotic nature and high stability with the Zn anodes. However, the ionic conductivity of nonaqueous electrolytes is relatively low compared to that of aqueous electrolytes. Most of the previous reviews focus only on the individual components of ZMBs. A review of ZMBs from a higher perspective, focusing on advanced ZMBs system design, is currently lacking.</p><p >In this Account, we begin with a brief overview of ZMBs, highlighting their advantages and current challenges. Subsequently, we give a summary of the development of inorganic cathodes (such as MnO<sub>2</sub>) for ZMBs. Specifically, development history and representative modification strategy of inorganic cathodes are illustrated. Following this, representative organic cathodes are discussed, along with introduction of novel modification str","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 4","pages":"599–611 599–611"},"PeriodicalIF":16.4,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428414","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":"Symmetry Breaking: Case Studies with Organic Cage-Racemates","authors":"Chenhao Chen,  and , Shaodong Zhang*, ","doi":"10.1021/acs.accounts.4c0075410.1021/acs.accounts.4c00754","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00754https://doi.org/10.1021/acs.accounts.4c00754","url":null,"abstract":"<p >Symmetry is a pervasive phenomenon spanning diverse fields, from art and architecture to mathematics and science. In the scientific realms, symmetry reveals fundamental laws, while symmetry breaking─the collapse of certain symmetry─is the underlying cause of phenomena. Research on symmetry and symmetry breaking consistently provides valuable insights across disciplines, from parity violation in physics to the origin of homochirality in biology. Chemistry is particularly rich in symmetry breaking studies, encompassing areas such as asymmetric synthesis, chiral resolution, chiral structure assembly, and so on. Across different disciplines, a well-defined methodology is fundamental and necessary to analyze the symmetry or symmetry breaking nature behind the phenomenon, enabling researchers to uncover the underlying principles and mechanisms. Basically, three key points underpin symmetry-related research: the scale-dependency of symmetry/symmetry breaking, the driving force behind symmetry breaking phenomena, and the properties arising from symmetry breaking.</p><p >This Account will focus on the three aforementioned key points elucidated with organic cages as proof-of-concept models, as organic cages exhibit shape-persistent 3D molecular frameworks, well-defined molecular motion, and a high propensity for crystallization.</p><p >First, we examine racemization processes of organic cages with dynamic molecular motions to illustrate that symmetry and symmetry breaking are time-scale-dependent. Specifically, the racemization, driven by molecular motion, is influenced by hydrogen bonding and the rigidity of the cage framework, which may or may not be observable within the experimental temporal scale. This determines whether the enantiomeric excess system, namely, the symmetry broken system, can be detected experimentally. We also investigate the hierarchical structures self-assembled by racemic organic cages, demonstrating that symmetry and asymmetry manifest differently across spatial scales, from molecular to supramolecular and macroscopic levels. Second, we discuss the driving force behind spontaneous chiral resolution─a classic symmetry-breaking event during crystallization─from a thermodynamic perspective. We suggest that racemic compounds, compared to conglomerates, are more entropy-favored, explaining their greater prevalence in nature. Spontaneous chiral resolution can take place only when a favorable enthalpy compensates for unfavorable entropy. In conglomerates composed of organic cages, strong intermolecular interactions along the screw axes provide the necessary compensation. Finally, we explore the unique properties that emerge from symmetry-broken molecular packing within crystals of cage racemates, such as second-harmonic generation and piezoelectricity. It turns out that the symmetry operation in molecular packing plays a critical role in determining material properties. By comprehensively analyzing symmetry and symmetry-breaking in ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 4","pages":"583–598 583–598"},"PeriodicalIF":16.4,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428422","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":"Heterogeneous Frustrated Lewis Pair Catalysts: Rational Structure Design and Mechanistic Elucidation Based on Intrinsic Properties of Supports","authors":"Jiasi Li, Guangchao Li* and Shik Chi Edman Tsang*, ","doi":"10.1021/acs.accounts.4c0068310.1021/acs.accounts.4c00683","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00683https://doi.org/10.1021/acs.accounts.4c00683","url":null,"abstract":"<p >The discovery of reversible hydrogenation using metal-free phosphoborate species in 2006 marked the official advent of frustrated Lewis pair (FLP) chemistry. This breakthrough revolutionized homogeneous catalysis approaches and paved the way for innovative catalytic strategies. The unique reactivity of FLPs is attributed to the Lewis base (LB) and Lewis acid (LA) sites either in spatial separation or in equilibrium, which actively react with molecules. Since 2010, heterogeneous FLP catalysts have gained increasing attention for their ability to enhance catalytic performance through tailored surface designs and improved recyclability, making them promising for industrial applications. Over the past 5 years, our group has focused on investigating and strategically modifying various types of solid catalysts with FLPs that are unique from classic solid FLPs. We have explored systematic characterization techniques to unravel the underlying mechanisms between the active sites and reactants. Additionally, we have demonstrated the critical role of catalysts’ intrinsic electronic and geometric properties in promoting FLP formation and stimulating synergistic effects. The characterization of FLP catalysts has been greatly enhanced by the use of advanced techniques such as synchrotron X-ray diffraction, neutron powder diffraction, X-ray photoelectron spectroscopy, extended X-ray absorption fine structure, elemental mapping in scanning transmission electron microscopy, electron paramagnetic resonance spectroscopy, diffuse-reflectance infrared Fourier transform spectroscopy, and solid-state nuclear magnetic resonance spectroscopy. These techniques have provided deeper insights into the structural and electronic properties of FLP systems for the future design of catalysts.</p><p >Understanding electron distribution in the overlapping orbitals of LA and LB pairs is essential for inducing FLPs in operando in heterogeneous catalysts through target electron reallocation by external stimuli. For instance, in silicoaluminophosphate-type zeolites with weak orbital overlap, the adsorption of polar gas molecules leads to heterolytic cleavage of the Al<sup>δ+</sup>–O<sup>δ−</sup> bond, creating unquenched LA–LB pairs. In a Ru-doped metal–organic framework, the Ru–N bond can be polarized through metal–ligand charge transfer under light, forming Ru<sup>+</sup>–N<sup>–</sup> pairs. This activation of FLP sites from the framework represents a groundbreaking innovation that expands the catalytic potential of existing materials. For catalysts already employing FLP chemistry to dynamically generate products from substrates, a complete mechanistic interpretation requires a thorough examination of the surface electronic properties and the surrounding environment. The hydrogen spillover ability on the Ru-doped FLP surfaces improves conversion efficiency by suppressing hydrogen poisoning at metal sites. In situ H<sub>2</sub>–H<sub>2</sub>O conditions enable the production of o","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 4","pages":"555–569 555–569"},"PeriodicalIF":16.4,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.accounts.4c00683","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428413","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aerolysin Nanopore Electrochemistry","authors":"Jun-Ge Li, Yi-Lun Ying* and Yi-Tao Long*, ","doi":"10.1021/acs.accounts.4c0063010.1021/acs.accounts.4c00630","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00630https://doi.org/10.1021/acs.accounts.4c00630","url":null,"abstract":"<p >Ions are the crucial signaling components for living organisms. In cells, their transportation across pore-forming membrane proteins is vital for regulating physiological functions, such as generating ionic current signals in response to target molecule recognition. This ion transport is affected by confined interactions and local environments within the protein pore. Therefore, the pore-forming protein can efficiently transduce the characteristics of each target molecule into ion-transport-mediated signals with high sensitivity. Inspired by nature, various protein pores have been developed into high-throughput and label-free nanopore sensors for single-molecule detection, enabling rapid and accurate readouts. In particular, aerolysin, a key virulence factor of <i>Aeromonas hydrophila</i>, exhibits a high sensitivity in generating ionic current fingerprints for detecting subtle differences in the sequence, conformation, and structure of DNA, proteins, polypeptides, oligosaccharides, and other molecules. Aerolysin features a cap that is approximately 14 nm wide on the <i>cis</i> side and a central pore that is about 10 nm long with a minimum diameter of around 1 nm. Its long lumen, with 11 charged rings at two entrances and neutral amino acids in between, facilitates the dwelling of the single analyte within the pore. This characteristic enables rich interactions between the well-defined residues within the pore and the analyte. As a result, the ionic current signal offers a unique molecular fingerprint, extending beyond the traditional volume exclusion model in nanopore sensing. In 2006, aerolysin was first reported to discriminate conformational differences of single peptides, opening the door for a rapidly growing field of aerolysin nanopore electrochemistry. Over the years, various mutant aerolysin nanopores have emerged, associated with advanced instrumentation and data analysis algorithms, enabling the simultaneous identification of over 30 targets with the number still increasing. Aerolysin nanopore electrochemistry in particular allows time-resolved qualitative and quantitative analysis ranging from DNA sequencing, proteomics, enzyme kinetics, and single-molecule reactions to potential clinical diagnostics. Especially, the feasibility of aerolysin nanopore electrochemistry in dynamic quantitative analysis would revolutionize omics studies at the single-molecule level, paving the way for the promising field of single-molecule temporal omics. Despite the success of this approach so far, it remains challenging to understand how confined interactions correlate to the distinguishable ionic signatures. Recent attempts have added correction terms to the volume exclusion model to account for variations in ion mobility within the nanopore caused by the confined interactions between the aerolysin and the analyte. Therefore, in this Account, we revisit the origin of the current blockade induced by target molecules inside the aerolysin nanopore.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 4","pages":"517–528 517–528"},"PeriodicalIF":16.4,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428412","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":"Skeletal Editing through Cycloaddition and Subsequent Cycloreversion Reactions","authors":"Pengwei Xu,  and , Armido Studer*, ","doi":"10.1021/acs.accounts.4c0081310.1021/acs.accounts.4c00813","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00813https://doi.org/10.1021/acs.accounts.4c00813","url":null,"abstract":"<p >Skeletal editing, which involves adding, deleting, or substituting single or multiple atoms within ring systems, has emerged as a transformative approach in modern synthetic chemistry. This innovative strategy addresses the ever-present demand for developing new drugs and advanced materials by enabling precise modifications of molecular frameworks without disrupting essential functional complexities. Ideally performed at late stages of synthesis, skeletal editing minimizes the need for the cost- and labor-intensive processes often associated with <i>de novo</i> synthesis, thus accelerating the discovery and optimization of complex molecular architectures. While current efforts in skeletal editing predominantly focus on monatomic-scale modifications, editing molecules through cycloaddition followed by cycloreversion offers a unique strategy to manipulate molecular frameworks on a double-atomic scale. This introduces new possibilities for chemical transformations and enables transformations such as double-atom transmutation, formal single-atom transmutation, and atom insertion. Early examples of such skeletal editing processes often relied on the inherent high reactivity of the substrates, which needed to be sufficiently active to undergo cycloaddition and possess good leaving groups for the subsequent fragmentation (cycloreversion) step. Recently, however, the structural editing of relatively inert substrates has become achievable through substrate activation strategies designed to enhance either the cycloaddition or subsequent cycloreversion step.</p><p >Along these lines, we recently developed a dearomative process for activating pyridines. In a simple high-yielding chemical operation, oxazinopyridines are readily obtained as activated dearomatized isolable intermediates. This method enabled us to achieve the transformation of pyridines into benzenes and naphthalenes through a cycloaddition/cycloreversion sequence. In this Account, related recent contributions from other research groups are highlighted as well, alongside early examples involving tetrazines, triazines, diazines, and other similar heterocycles as cycloaddition reaction partners. By offering a streamlined route to modify molecular structures, these approaches have demonstrated their ability to interconvert arenes and heteroarenes and have shown significant potential for late-stage editing applications as well as advancing drug discovery and the synthesis of bioactive molecules.</p><p >In the future, these approaches will undoubtedly see broader development in the field of skeletal editing. New strategies for substrate activation should be devised to enable not only the incorporation of nitrogen and other heteroatoms into rings─rather than their deletion─but also to achieve ring contraction and expand the application of this strategy to non-aromatic rings. We hope that the advancements summarized in this Account will inspire chemists to explore and expand skeletal editing method","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 4","pages":"647–658 647–658"},"PeriodicalIF":16.4,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428373","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":"Computational Modeling of Electrocatalysts for CO2 Reduction: Probing the Role of Primary, Secondary, and Outer Coordination Spheres","authors":"Christina M. Zeng,  and , Julien A. Panetier*, ","doi":"10.1021/acs.accounts.4c0063110.1021/acs.accounts.4c00631","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00631https://doi.org/10.1021/acs.accounts.4c00631","url":null,"abstract":"<p >In the search for efficient and selective electrocatalysts capable of converting greenhouse gases to value-added products, enzymes found in naturally existing bacteria provide the basis for most approaches toward electrocatalyst design. Ni,Fe-carbon monoxide dehydrogenase (Ni,Fe-CODH) is one such enzyme, with a nickel–iron–sulfur cluster named the C-cluster, where CO<sub>2</sub> binds and is converted to CO at high rates near the thermodynamic potential. In this Account, we divide the enzyme’s catalytic contributions into three categories based on location and function. We also discuss how computational techniques provide crucial insight into implementing these findings in homogeneous CO<sub>2</sub> reduction electrocatalysis design principles. The CO<sub>2</sub> binding sites (e.g., Ni and “unique” Fe ion) along with the ligands that support it (e.g., iron–sulfur cluster) form the primary coordination sphere. This is replicated in molecular electrocatalysts via the metal center and ligand framework where the substrate binds. This coordination sphere has a direct impact on the electronic configuration of the catalyst. By computationally modeling a series of Ni and Co complexes with bipyridyl-<i>N</i>-heterocyclic carbene ligand frameworks of varying degrees of planarity, we were able to closely examine how the primary coordination sphere controls the product distribution between CO and H<sub>2</sub> for these catalysts. The secondary coordination sphere (SCS) of Ni,Fe-CODH contains residues proximal to the active site pocket that provide hydrogen-bonding stabilizations necessary for the reaction to proceed. Enhancing the SCS when synthesizing new catalysts involves substituting functional groups onto the ligand for direct interaction with the substrate. To analyze the endless possible substitutions, computational techniques are ideal for deciphering the intricacies of substituent effects, as we demonstrated with an array of imidazolium-functionalized Mn and Re bipyridyl tricarbonyl complexes. By examining how the electrostatic interactions between the ligand, substrate, and proton source lowered activation energy barriers, we determined how best to pinpoint the SCS additions. The outer coordination sphere comprises the remaining parts of Ni,Fe-CODH, such as the elaborate protein matrix, solvent interactions, and remote metalloclusters. The challenge in elucidating and replicating the role of the vast protein matrix has understandably led to a localized focus on the primary and secondary coordination spheres. However, certain portions of Ni,Fe-CODH’s expansive protein scaffold are suggested to be catalytically relevant despite considerable distance from the active site. Closer studies of these relatively overlooked areas of nature’s exceptionally proficient catalysts may be crucial to continually improve upon electrocatalysis protocols. Mechanistic analysis of cobalt phthalocyanines (CoPc) immobilized onto carbon nanotubes (CoPc/CNT) reveals h","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 3","pages":"342–353 342–353"},"PeriodicalIF":16.4,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143089559","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":"Development of PFAS-Free Locally Concentrated Ionic Liquid Electrolytes for High-Energy Lithium and Aluminum Metal Batteries","authors":"Xu Liu, Cheng Xu, Henry Adenusi, Yuping Wu* and Stefano Passerini*, ","doi":"10.1021/acs.accounts.4c0065310.1021/acs.accounts.4c00653","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00653https://doi.org/10.1021/acs.accounts.4c00653","url":null,"abstract":"<p >Lithium-ion batteries (LIBs) based on graphite anodes are a widely used state-of-the-art battery technology, but their energy density is approaching theoretical limits, prompting interest in lithium-metal batteries (LMBs) that can achieve higher energy density. In addition, the limited availability of lithium reserves raises supply concerns; therefore, research on postlithium metal batteries is underway. A major issue with these metal anodes, including lithium, is dendritic formation and insufficient reversibility, which leads to safety risks due to short circuits and the use of flammable electrolytes.</p><p >Ionic liquid electrolytes (ILEs), composed of metal salts and ionic liquids, offer a safer alternative due to their nonflammable nature and high thermal stability. Moreover, they can enable high Coulombic efficiency (CE) for lithium metal anodes (LMAs) and allow reversible stripping/plating of various post-lithium metals for battery application, e.g., aluminum metal batteries (AMBs). Despite these advantages, ILEs suffer from high viscosity, which impairs ion transport and wettability. To resolve these challenges, researchers have developed locally concentrated ionic liquid electrolytes (LCILEs) by adding low-viscosity nonsolvating cosolvents, e.g., hydrofluoroether, to ILEs. These cosolvents do not coordinate with cationic charge carriers, thereby reducing viscosity and improving ion transport without compromising the compatibility of electrolytes with metal anodes. However, due to the inherent difference of molecular organic solvents and ionic liquids full of charged species, the most used nonsolvating cosolvents, i.e., hydrofluoroether, are less effective for ILEs with respect to concentrated electrolytes based on conventional organic solvents. Moreover, hydrofluoroether contains environmentally problematic −CF<sub>3</sub> and/or −CF<sub>2</sub>- groups, i.e., per- and polyfluoroalkyl substances (PFAS), with their use subject to restrictions.</p><p >In this Account, we provide an overview of the endeavors of our research group on the development of PFAS-free LCILEs for high-energy LMBs and AMBs. First, aromatic organic cations and aromatic less/nonfluorinated cosolvents are proposed to weaken the organic cation–anion interaction and strengthen the organic cation-cosolvent interaction, respectively. This is with consideration of the uncovered phase nanosegregation structure of LCILEs that effectively reduces the viscosity and promotes the Li<sup>+</sup> transport ability with respect to the conventional nonaromatic organic cations and highly fluorinated PFAS cosolvents. Then, the effect of electrolyte components that do not coordinate to Li<sup>+</sup>, including organic cations and nonsolvating cosolvents, on the SEI composition and LMA reversibility is presented, which confirms the feasibility of reaching a high lithium stripping/plating CE up to 99.7% in the developed PFAS-free LCILEs. In the subsequent discussion on cathode compati","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"58 3","pages":"354–365 354–365"},"PeriodicalIF":16.4,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.accounts.4c00653","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143089640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of PFAS-Free Locally Concentrated Ionic Liquid Electrolytes for High-Energy Lithium and Aluminum Metal Batteries","authors":"Xu Liu, Cheng Xu, Henry Adenusi, Yuping Wu, Stefano Passerini","doi":"10.1021/acs.accounts.4c00653","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00653","url":null,"abstract":"Lithium-ion batteries (LIBs) based on graphite anodes are a widely used state-of-the-art battery technology, but their energy density is approaching theoretical limits, prompting interest in lithium-metal batteries (LMBs) that can achieve higher energy density. In addition, the limited availability of lithium reserves raises supply concerns; therefore, research on postlithium metal batteries is underway. A major issue with these metal anodes, including lithium, is dendritic formation and insufficient reversibility, which leads to safety risks due to short circuits and the use of flammable electrolytes.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"63 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143035160","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":"Elucidating the Origins of High Capacity in Iron-Based Conversion Materials: Benefit of Complementary Advanced Characterization toward Mechanistic Understanding","authors":"Ryan C. Hill, Kenneth J. Takeuchi","doi":"10.1021/acs.accounts.4c00717","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00717","url":null,"abstract":"Lithium-ion batteries are recognized as an important electrochemical energy storage technology due to their superior volumetric and gravimetric energy densities. Graphite is widely used as the negative electrode, and its adoption enabled much of the modern portable electronics technology landscape. However, developing markets, such as electric vehicles and grid-scale storage, have increased demands, including higher energy content and a diverse materials supply chain. Alternatives that provide the opportunity to increase capacity and address supply chain concerns are of interest.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":"49 1","pages":""},"PeriodicalIF":18.3,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143030721","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}