ACS Energy Letters 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 and Arthur G. Suits*, ","doi":"10.1021/acs.accounts.4c0048910.1021/acs.accounts.4c00489","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00489https://doi.org/10.1021/acs.accounts.4c00489","url":null,"abstract":"<p >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 10<sup>16</sup>–10<sup>18</sup> cm<sup>–3</sup> 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.</p><p >In this Account, we review recent advances made using the CPUF technique, including studies of photodissociation, radical–radical reaction dynamics, and low temperature kinetics. These studies highlight both the strength of universal and multiplexed detection and the challenges of coupling it to a high-density collisional environment. Product branching and product evolution as a function of time have been measured for astrochemically relevant systems, relying on the detailed characterization of these flow conditions via experiments and fluid dynamics simulations. In the photodissociation of isoxazole, an unusual heterocyclic molecule with a very low-energy conical intersection, we have identified 7 products in 5 reaction channels and determined the product branching, pointing to both direct and indirect pathways. We have also approached the same system from separated NO and C<sub>3</sub>H<sub>3</sub> reactants to explore a broader range of the potential energy surface, demonstrating the power of multichannel branching measurements for complex radical–radical reactions. We determined the product branching in the C<sub>3</sub>H<sub>2</sub> isomers in the photodissociation of the propargyl radical and identified the importance of a hydrogen atom catalyzed isomerization to the lowest energy cyclic form. This then motivated a study of direct D-H exchange reaction in radicals, in which we demonstrate that it is an important and overlooked pathway for deuterium fractionation in astrochemical environments. Recently, we have shown the measurement of low temperature kinetics inside an ","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"57 21","pages":"3126–3137 3126–3137"},"PeriodicalIF":16.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Consequences of Annealing on Metal–Insulator–Semiconductor Water Splitting Photoelectrocatalysts","authors":"John Hemmerling, Aarti Mathur, Suljo Linic","doi":"10.1021/acsenergylett.4c02337","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02337","url":null,"abstract":"Metal–insulator–semiconductor (MIS) systems, combining light-harvesting semiconductors with electrocatalytic metals, are promising photoelectrocatalysts for efficient and stable photoelectrochemical water splitting. Despite considerable advancements, MIS systems fall significantly below the theoretical photovoltage limits. Important hurdles are the (1) presence of interfacial defects that serve as charge recombination centers and (2) insufficient charge carrier selectivity of the insulators. In this study, we investigate thermal annealing to overcome these obstacles. The impact of annealing is demonstrated by comparing the oxygen evolution reaction (OER) performance of two MIS systems that employ common insulators (Al₂O₃ vs HfO₂) in Ir/Si photoelectrocatalysts. Experimental and modeling results reveal an elaborate interplay between underlying mechanisms at different annealing conditions. We demonstrate how to quantify these mechanisms, showing that annealing can significantly improve performance by passivating interfacial defects but can also impair the insulators’ charge tunneling characteristics. Insights from this study offer direction toward approaching the maximum photovoltage in MIS photoelectrocatalysts.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"3 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431530","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","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*,  and , Satoshi Horike*, ","doi":"10.1021/acs.accounts.4c0051910.1021/acs.accounts.4c00519","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00519https://doi.org/10.1021/acs.accounts.4c00519","url":null,"abstract":"<p >The conversion of carbon dioxide (CO<sub>2</sub>) to value-added functional materials is a major challenge in realizing a carbon-neutral society. Although CO<sub>2</sub> is an attractive renewable carbon resource with high natural abundance, its chemical inertness has made the conversion of CO<sub>2</sub> 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 CO<sub>2</sub> into MOF/COFs have been unexplored due to the lack of synthetic guidelines for converting CO<sub>2</sub> into molecular-based building units.</p><p >In this Account, we describe state-of-the-art studies on the conversion of CO<sub>2</sub> into MOF/COFs. First, we outline the key design principles of CO<sub>2</sub>-derived molecular building units for the construction of porous structures. The appropriate design of reactivity and the positioning of bridging sites in CO<sub>2</sub>-derived molecular building units is essential for constructing CO<sub>2</sub>-derived MOF/COFs with desired structures and properties. The synthesis of CO<sub>2</sub>-derived MOF/COFs involves both the transformation of CO<sub>2</sub> into building units and the formation of extended structures of the MOF/COFs. We categorized the synthetic methods into three types as follows: a one-step synthesis (<i>Type-I</i>); a one-pot synthesis without workup (<i>Type-II</i>); and a multistep synthesis which needs workup (<i>Type-III</i>).</p><p >We demonstrate that borohydride can convert CO<sub>2</sub> into formate and formylhydroborate that serve as a bridging linker for MOFs in the Type-I and Type-II synthesis, representing the first examples of CO<sub>2</sub>-derived MOFs. The electronegativity of coexisting metal ions determines the selective conversion of CO<sub>2</sub> into formate and formylhydroborate. Formylhydroborate-based MOFs exhibit flexible pore sizes controlled by the pressure of CO<sub>2</sub> during synthesis. In pursuit of highly porous structures, we present the Type-I synthesis of MOFs from CO<sub>2</sub> via the in situ transformation of CO<sub>2</sub> into carbamate linkers by amines. The direct conversion of diluted CO<sub>2</sub> (400 ppm) in air into carbamate-based MOFs is also feasible. Coordination interactions stabilize the intrinsically labile carbamate in the MOF lattice. A recent study demonstrates that the Type-III synthesis using alkynylsilane precursors enables the synthesis of highly porous and stable carboxylate-based MOFs from CO<sub>2</sub>, which exhibit catalytic activity in CO<sub>2</sub> conversion. We also extended the synthesis of MOFs from CO<sub>2</sub> to COFs. The Type-III synthesis using a formamide monomer affords stable CO<sub>2</sub>-derived COFs","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"57 21","pages":"3206–3216 3206–3216"},"PeriodicalIF":16.4,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.accounts.4c00519","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577536","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemomechanical Pairing of Alloy Anodes and Solid-State Electrolytes","authors":"Shiwei Chen, Qingbo Cao, Bin Tang, Xinyu Yu, Zhen Zhou, Shou-Hang Bo, Yunlong Guo","doi":"10.1021/acsenergylett.4c01983","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01983","url":null,"abstract":"Alloy anodes present promising alternatives to alkali metals in solid-state batteries but still face morphological instability upon cycling. Unlike conventional batteries using liquid electrolytes, interfacial evolution between solid-state electrolytes and alloy anodes is determined by interfacial electrochemistry and mechanics. Here, we adapt a classical chemomechanical model for Li metal to apply to alloy anodes. This allows generalizing a principle, namely, the hard and soft electrolytes and alloy anodes pairing principle, to guide improving morphological stability. Specifically, “hard” (high-shear-modulus) ceramic electrolytes should be paired with “harder” alloys, while “soft” (low-shear-modulus) polymer electrolytes favor “softer” alloys. We examine the chemomechanical properties of several Li–M alloys (M = Al, Mg, In, Sn, and Sb). Consistent with the principle, the “harder” Li–Sn anode exhibits a flattened morphology with the “hard” Li₆PS₅Cl electrolyte after cycling. Conversely, the “softer” Li–In anode evolves extremely rough, indicating Li–In dendrite formation. Our work underscores the significance of tuning alloy anode mechanical properties, incorporating well-established rules in traditional metallurgy.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"24 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Emerging All-Solid-State Lithium–Sulfur Batteries: Holy Grails for Future Secondary Batteries","authors":"Yang-Kook Sun","doi":"10.1021/acsenergylett.4c02563","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02563","url":null,"abstract":"Figure 1. Forecasted cell-level energy densities and costs of ASSLSBs compared to those of other battery types, such as LIBs and ASSBs. The energy density and cost of each battery type are plotted based on values reported in recent literature: LIBs (NCM), (20,21) LIBs (LiFePO₄ (LFP)), (21−23) and ASSBs. (24−26) The expected values of 1 and 2 for the cell energy densities of ASSLSBs were calculated assuming composite cathodes with respective S contents of 50 and 60 wt%, respective levels of S utilization of 80% and 90% (relative to their theoretical capacities), and cell potentials of 2.0 V. Additionally, it was assumed that the composite cathodes constituted 30 wt% of the total cell masses. This article references 36 other publications. This article has not yet been cited by other publications.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"65 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemical Roadmap toward Stable Electrolyte–Electrode Interfaces in All-Solid-State Batteries","authors":"Chuhong Wang, Siwen Wang, Chen Ling","doi":"10.1021/acsenergylett.4c01618","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01618","url":null,"abstract":"All-solid-state batteries (ASSBs) hold significant promise for enhanced safety, energy density, and power density compared to conventional lithium-ion batteries. However, their development is impeded by the growth of resistance and diminished cell performance due to the interfacial reactivity between the electrodes and solid-state electrolytes. Comprehensive knowledge of interface reactions and effective mitigation strategies are essential to unlock the potential of ASSBs. Herein, we introduce the concept of a stability network to encode chemical and electrochemical reactions among lithium and non-lithium compounds within a comprehensive and complex network structure. Through analyzing the topological structure of the stability network, we reveal an organized and chemically instructive pattern of two-phase reactions and equilibria under different electrochemical conditions. This understanding of intrinsic patterns in relation to compositional, chemical, and electrochemical variables offers a set of principles for the experimental design and engineering of interfaces, serving as a chemical roadmap for achieving stable electrolyte–electrode interfaces in ASSBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"40 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"LiF in Inverted Perovskite Solar Cells: Dipole or Doping?","authors":"Seung-Gu Choi, Sung-Kwang Jung, Joo-Hong Lee, Jae-Hwan Kim, Wenting Zheng, Jin-Wook Lee","doi":"10.1021/acsenergylett.4c02000","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02000","url":null,"abstract":"The functions and mechanisms of thermally evaporated lithium fluoride, widely acknowledged for its role in passivating the perovskite surface as a dipole interlayer, remain not fully elucidated. This work reveals the beneficial effects of LiF originating from interstitial incorporation of lithium cations in the underlying perovskite layer.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"77 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405462","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Li+ Conduction of Soft-Base Anion-Immobilized Covalent Organic Frameworks for All-Solid-State Lithium–Metal Batteries","authors":"Rak Hyeon Choi, Jungjeong So, Younghun Kim, Dongwhan Lee, Hye Ryung Byon","doi":"10.1021/acsenergylett.4c01941","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01941","url":null,"abstract":"Organic solid-state electrolytes (SSEs) offer improved safety and flexibility, but they face challenges with low ionic conductivity at room temperature. Covalent organic frameworks (COFs) present a promising solution by preventing segmental motion and facilitating Li⁺ ion transfer through nanoporous channels with regularly aligned anionic groups. In particular, dissociating Li⁺ ions from these immobilized anionic groups is crucial for increasing Li⁺ ion conductivity. However, the design of COFs with electron-delocalized and soft bases, such as fluorinated sulfonimides anionic groups, for easier Li⁺ dissociation has been hindered by the challenging synthesis of these building blocks. Here, we successfully synthesized sulfonyl(trifluoromethanesulfonyl)imide (TFSI^–)-functionalized COFs and demonstrated a remarkable Li⁺ ion conductivity of 7.65 × 10^–5 S cm^–1 at 25 °C, which surpasses all known organic SSEs. This single Li⁺ ion conductor achieved over 200 times cyclability in Li and LiFePO₄ cells, representing a substantial step toward developing better organic SSEs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"228 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polaron-Based Electronic Conduction in Mixed Ionic-Electronic Conducting Lithium Garnets","authors":"Charles E. Schwarz, Ramanuja Srinivasan Saravanan, Nina M. Borodin, Yunsheng Liu, Eric D. Wachsman, Yifei Mo","doi":"10.1021/acsenergylett.4c02060","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c02060","url":null,"abstract":"Recent research has demonstrated that doped lithium garnet compositions with mixed ionic–electronic conducting (MIEC) properties can significantly enhance the performance of solid-state batteries with lithium metal anodes. However, the mechanisms that enable electronic conduction in these garnets are not well understood. In this study, we conduct first-principles calculations to investigate the polaron-based mechanism of electronic conduction in these MIEC garnets. We model polaron trapping on multivalent cation dopants in the lithium garnet structure and estimate the energy barriers for site-to-site polaron migration. By analyzing defect formation energies and cation charge transitions, we elucidate why certain cations and cation combinations greatly enhance the electronic conductivity in lithium garnets. Our computations lead to suggestions for new cation dopants and new strategies to further improve MIEC garnets in high-performance solid-state batteries. The study can serve as a general framework to guide the further development of novel MIEC materials for energy technologies.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"316 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","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,&nbsp;Gihyun Lee and Moonhyun Oh*,&nbsp;","doi":"10.1021/acs.accounts.4c0046910.1021/acs.accounts.4c00469","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00469https://doi.org/10.1021/acs.accounts.4c00469","url":null,"abstract":"<p >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.</p>","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"57 21","pages":"3113–3125 3113–3125"},"PeriodicalIF":16.4,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142577531","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}