Accounts of materials research最新文献

{"title":"Layered Transition Metal Carbides/Nitrides: From Chemical Etching to Chemical Editing","authors":"Haoming Ding, Youbing Li, Mian Li, Zhifang Chai, Qing Huang","doi":"10.1021/accountsmr.4c00250","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00250","url":null,"abstract":"Topotactic transformations between related crystal structures, involving etching, replacement, and intercalation, are increasingly recognized in the design and tuning of material properties. These transformations reveal the fundamental principles of material structural changes, paving the way for creating novel materials with unique properties. Layered materials readily undergo structural or compositional changes due to their stacked atomic layers and bonding features. MAX phases, as nonvan der Waals (non-vdW) layered compounds, exhibit distinctive elemental compositions and bonding characters that make them suitable for topotactic transformations. A notable example is the typical transformation from MAX phases to MXenes, a new addition to two-dimensional (2D) materials, through A-site etching within MAX phases. In turn, the 2D structure of MXenes further promoted versatile topotactic transformations utilizing the interlayer space and tunable surfaces. This Account comprehensively reviews the topotactic transformation in MXenes and MAX phases, covering aspects from chemical etching to versatile chemical editing. We commence with an analysis of MAX phase degradation, examining the corrosion resistance of MAX phases in liquid metals and molten salts, which is crucial for their application as nuclear materials. This leads us to introduce the novel concept of precise A-site etching in MAX phases, which has paved the way for the groundbreaking discovery of 2D MXene. Given the important effect of etching methods on MXenes, we then delve into the various etching methods employed in preparing MXene and explore the detailed processes and mechanisms behind each method. Additionally, we highlight the recent advancements made by our research group regarding the Lewis acidic molten salt (LAMS) method. This method utilizes LAMSs as etching agents to selectively etch the A-site atomic layer, creating opportunities for the subsequent intercalation of atoms or anions to achieve isomorphous replacement of A-site atoms and surface modification with novel terminations. The strong oxidation ability of LAMSs also offers versatility in selectively etching A-site atomic species, particularly confined to the Al element. The LAMS method shows potential for synthesizing and controlling the structure of MXene and MAX phases, albeit with limitations. Its success depends on the properties of LAMSs, which must facilitate both etching and intercalation. However, some LAMSs are unsuitable due to their low redox potential, low boiling points, and instability at high temperatures. Therefore, we propose a versatile chemical scissor-mediated structural editing strategy. This strategy decouples etching from intercalation, using Lewis acidic cations or reduced metal atoms as chemical scissors to create space between MX sublayers, allowing atoms or anions to diffuse and enable topotactic transitions. This approach has facilitated the intercalation of various A-site atoms, expanded MXen","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Optimizing Solvent Chemistry for High-Quality Halide Perovskite Films","authors":"Xiaofeng Huang, Binghui Wu, Nanfeng Zheng","doi":"10.1021/accountsmr.4c00148","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00148","url":null,"abstract":"Over the past decade, solution-processed organic–inorganic hybrid perovskite solar cells (PSCs) have emerged as a viable alternative to traditional crystalline silicon photovoltaics, with power conversion efficiency (PCE) increasing notably from 3.8% to over 26%. This remarkable advancement is attributed to the unique band structures and exceptional defect tolerance of the hybrid perovskites. The bandgaps in perovskites derive from their antibonding orbitals at both the valence band maximum and conduction band minimum. Consequently, bond breaking creates states away from the bandgap, resulting in either shallow defects or states within the valence band. Despite defect densities up to 10<sup>6</sup> times higher than single-crystal silicon, polycrystalline perovskite films (<1 μm thick) can still achieve comparable device performance due to their high defect tolerance. Superior photovoltaic performance in perovskite films depends on an efficient wet-chemical process, offering a notable advantage over silicon-based photovoltaic technology. Evidently, solvent characteristics and their potential interaction with perovskites significantly impact crystal growth from precursor inks, subsequent polycrystalline film quality, and the ultimate performance of devices. Understanding solvent properties in relation to film formation processes is essential for informing solvent selection in the emerging perovskite photovoltaics and its future commercialization. In this Account, we present a thorough analysis of solution-processed perovskite films, encompassing the crystallization process and phase transition of perovskite-related solvated complexes, and structure passivation of perovskite phase. We systematically categorize the prevalent solvents utilized in film preparation and outline a solvent roadmap for producing high-quality perovskite films from a chemical perspective, considering their interaction with the perovskite structure. We also address often-overlooked factors in solvent selection in current research. First, middle-polarity dispersion solvents fundamentally govern nucleation and growth kinetics of perovskite solvated films in the solution phase, thereby significantly shaping film morphology. However, control over the solvation interaction between dispersion solvent and perovskite structure for morphology regulation remains insufficient. Second, high-polarity binding solvents interact with the perovskite structure via solvent-involved intermediates, optimizing crystallization kinetics in the solution phase (sol–gel state) and controlling phase-transition kinetics of the intermediate phase. This interaction influences the crystal and structural properties of the resultant perovskite phase though managing the intermediate phase remains challenging. Third, low-polarity modification solvents, combined with functional passivation molecules, are employed to modulate interface energetics of perovskite films by enabling both chemical defect passivation","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Optimization Strategies for Cathode Materials in Lithium–Oxygen Batteries","authors":"Shang-Qi Li, Jia-Ning Yang, Kai-Xue Wang, Jie-Sheng Chen","doi":"10.1021/accountsmr.4c00167","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00167","url":null,"abstract":"Developing high energy density, low-cost, and safe batteries remains a constant challenge that not only drives technological innovation but also holds the potential to transform human lifestyles. Although lithium-ion batteries have been widely adopted, their theoretical energy density is nearing its limit. Consequently, there is an urgent need to explore and investigate other battery systems with higher power capacities to propel technological advancements in this field. In this context, metal–oxygen batteries have attracted considerable interest because of their exceptionally high theoretical energy densities. Among the various metal–oxygen batteries, lithium–oxygen (Li–O<sub>2</sub>) batteries stand out for their highest thermodynamic equilibrium potential (∼2.96 V) and greatest theoretical specific energy (∼3500 Wh kg<sup>–1</sup>), positioning them as a promising avenue for future energy storage advancements. Over the past few decades, global scientists have conducted extensive research into the electrochemical reaction mechanisms, material sciences, and system designs of Li–O<sub>2</sub> batteries (LOBs), achieving numerous significant breakthroughs. Despite these remarkable advancements, research on LOBs is still in its infancy, confronting numerous unresolved critical issues. First, the deposition of Li<sub>2</sub>O<sub>2</sub> on the electrode surface severely hinders further electrochemical reactions, resulting in actual discharge capacities that are far below theoretical values. Second, the kinetics of the oxygen electrode reactions are relatively slow, failing to meet high power demands and inducing severe polarization phenomena, which significantly reduces energy efficiency. Last, byproducts generated during the charge/discharge process lead to the degradation of electrode materials and electrolytes, markedly shortening the cycle life of the battery. The rational design of efficient and durable catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is considered one of the most effective strategies for overcoming the aforementioned obstacles. In this Account, we summarize the major electronic modulation strategies for developing efficient cathode catalysts, including structural design, composite material construction, surface and interface engineering, and heteroatom doping. First, specific methods to enhance catalyst performance through optimizing material morphology and structural design are discussed. Then, the construction of composite materials is presented to highlight the synergistic effects of various components in improving battery performance. Next, surface and interface engineering, which could regulate charge transfer and reaction activity, is outlined. Finally, the function of heteroatom doping in enhancing catalytic activity and stability by modifying the electronic structure of catalysts is summarized. Building on the optimization of the performance and reliability of each component in LOB","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142596742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Activation and Catalysis of Methane over Metal–Organic Framework Materials","authors":"Bing An, Yujie Ma, Xue Han, Martin Schröder, Sihai Yang","doi":"10.1021/accountsmr.4c00279","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00279","url":null,"abstract":"Methane (CH₄), which is the main component of natural gas, is an abundant and widely available carbon resource. However, CH₄ has a low energy density of only 36 kJ L^–1 under ambient conditions, which is significantly lower than that of gasoline (<i>ca</i>. 34 MJ L^–1). The activation and catalytic conversion of CH₄ into value-added chemicals [<i>e.g</i>., methanol (CH₃OH), which has an energy density of <i>ca</i>. 17 MJ L^–1], can effectively lift its energy density. However, this conversion is highly challenging due to the inert nature of CH₄, characterized by its strong C–H bonds and high stability. Consequently, the development of efficient materials that can optimize the binding and activation pathway of CH₄ with control of product selectivity has attracted considerable recent interest. Metal–organic framework (MOF) materials have emerged as particularly attractive candidates for the development of efficient sorbents and heterogeneous catalysts due to their high porosity, low density, high surface area and structural versatility. These properties enable MOFs to act as effective platforms for the adsorption, binding and catalytic conversion of CH₄ into valuable chemicals. Recent reports have highlighted MOFs as promising materials for these applications, leading to new insights into the structure–activity relationships that govern their performance in various systems.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"146 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Data-Driven Combinatorial Design of Highly Energetic Materials","authors":"Linyuan Wen, Yinglei Wang, Yingzhe Liu","doi":"10.1021/accountsmr.4c00230","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00230","url":null,"abstract":"In this Account, we present a comprehensive overview of recent advancements in applying data-driven combinatorial design for developing novel high-energy-density materials. Initially, we outline the progress in energetic materials (EMs) development within the framework of the four scientific paradigms, with particular emphasis on the opportunities afforded by the evolution of computer and data science, which has propelled the theoretical design of EMs into a new era of data-driven development. We then discuss the structural features of typical EMs such as TNT, RDX, HMX, and CL-20, namely, a “scaffolds + functional groups” characteristic, underscoring the efficacy of the combinatorial design approach in constructing novel EMs. It has been discerned that those modifications to the scaffolds are the primary driving force behind the enhancement of EMs’ properties.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"67 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142579959","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"UCl3-Type Solid Electrolytes: Fast Ionic Conduction and Enhanced Electrode Compatibility","authors":"Yi-Chen Yin, Jin-Da Luo, Hong-Bin Yao","doi":"10.1021/accountsmr.4c00073","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00073","url":null,"abstract":"Figure 1. Origin of the superionic conduction of UCl&lt;sub&gt;3&lt;/sub&gt;-type SEs with the non-close-packed framework. (a) Li&lt;sup&gt;+&lt;/sup&gt; probability density, represented by green isosurfaces from AIMD simulations in the vacancy-contained LaCl&lt;sub&gt;3&lt;/sub&gt; lattice. Reproduced with permission from reference (21). Copyright 2023 the author(s), under exclusive license to Springer Nature Limited. (b) Schematic of diffusion channel. Reproduced with permission from reference (24). Copyright 2024 John Wiley and Sons. (c) Diffusion channel size distribution of Li&lt;sub&gt;3&lt;/sub&gt;YCl&lt;sub&gt;6&lt;/sub&gt;, Li&lt;sub&gt;3&lt;/sub&gt;InCl&lt;sub&gt;6&lt;/sub&gt;, LiNbOCl&lt;sub&gt;4&lt;/sub&gt;, and UCl&lt;sub&gt;3&lt;/sub&gt;-type Li&lt;sub&gt;0.388&lt;/sub&gt;Ta&lt;sub&gt;0.238&lt;/sub&gt;La&lt;sub&gt;0.475&lt;/sub&gt;Cl&lt;sub&gt;3&lt;/sub&gt; (LTLC). Reproduced with permission from reference (24). Copyright 2024 John Wiley and Sons. (d) Schematic illustration of the effects of inherent distortion on energy landscape. Reproduced with permission from reference (24). Copyright 2024 John Wiley and Sons. Figure 2. Ionic conductivity values at room temperature of crystalline chloride SEs, including conventional close-packed Li&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt;M&lt;sub&gt;&lt;i&gt;y&lt;/i&gt;&lt;/sub&gt;Cl&lt;sub&gt;&lt;i&gt;n&lt;/i&gt;&lt;/sub&gt; SEs and UCl&lt;sub&gt;3&lt;/sub&gt;-type LaCl&lt;sub&gt;3&lt;/sub&gt;-based SEs. (1−4,10−14,21) Reproduced with permission from reference (21). Copyright 2023 the author(s), under exclusive license to Springer Nature Limited. Figure 3. UCl&lt;sub&gt;3&lt;/sub&gt;-type SEs with a more stable interface toward lithium metal anode. (a) Depth-dependent La 3d&lt;sub&gt;5/2&lt;/sub&gt; X-ray photoelectron spectroscopy (XPS) spectra of the interface of Li&lt;sub&gt;0.388&lt;/sub&gt;Ta&lt;sub&gt;0.238&lt;/sub&gt;La&lt;sub&gt;0.475&lt;/sub&gt;Cl&lt;sub&gt;3&lt;/sub&gt; SE after 50 h of cycling. Reproduced with permission from reference (21). Copyright 2023 by Springer Nature Limited. (b) Depth-dependent La 3d&lt;sub&gt;5/2&lt;/sub&gt; XPS spectra of the interface of Li&lt;sub&gt;0.388&lt;/sub&gt;Ta&lt;sub&gt;0.238&lt;/sub&gt;La&lt;sub&gt;0.475&lt;/sub&gt;Cl&lt;sub&gt;3&lt;/sub&gt; SE after 50 h of cycling. Reproduced with permission from reference (21). Copyright 2023 the author(s), under exclusive license to Springer Nature Limited. (c) Voltage profile of a Li/Li&lt;sub&gt;0.388&lt;/sub&gt;Ta&lt;sub&gt;0.238&lt;/sub&gt;La&lt;sub&gt;0.475&lt;/sub&gt;Cl&lt;sub&gt;3&lt;/sub&gt;/Li symmetric cell cycled under a current density of 0.2 mA cm&lt;sup&gt;–2&lt;/sup&gt; and areal capacity of 1 mAh cm&lt;sup&gt;–2&lt;/sup&gt; at 30 °C. Insets: corresponding magnified voltage profiles indicate steady Li plating/stripping voltages. Reproduced with permission from reference (21). Copyright 2023 the author(s), under exclusive license to Springer Nature Limited. (d) La 3d&lt;sub&gt;5/2&lt;/sub&gt; (left) and Zr 3d (right) XPS spectra of the Li|Li&lt;sub&gt;0.8&lt;/sub&gt;Zr&lt;sub&gt;0.25&lt;/sub&gt;La&lt;sub&gt;0.5&lt;/sub&gt;Cl&lt;sub&gt;2.7&lt;/sub&gt;O&lt;sub&gt;0.3&lt;/sub&gt; interface after 500 h cycling, respectively. Reproduced with permission from reference (23). Copyright 2024 Royal Society of Chemistry. (e) Comparison of the critical current density (CCD) of Li metal symmetric cells with different solid electrolytes (Ga-LLZO (Li&lt;sub&gt;6.4&lt;/sub&gt;Ga&lt;sub&gt;0.2&lt;/sub&gt;La&lt;sub&gt;3&lt;/sub&gt;Zr&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;12&lt;/sub&gt;); ","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"12 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Methodologies to Improve the Stability of High-Efficiency Perovskite Solar Cells","authors":"Sanjay Sandhu, Nam-Gyu Park","doi":"10.1021/accountsmr.4c00237","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00237","url":null,"abstract":"Organic–inorganic lead halide perovskite solar cells (PSCs) have attracted significant interest from the photovoltaic (PV) community due to suitable optoelectronic properties, low manufacturing cost, and tremendous PV performance with a certified power conversion efficiency (PCE) of up to 26.5%. However, long-term operational stability should be guaranteed for future commercialization. Over the past decade, intensive research has focused on improving the PV performance and device stability through the development of novel charge transport materials, additive engineering, compositional engineering, interfacial modifications, and the synthesis of perovskite single crystals. In this Account, we provide a comprehensive overview of recent progress and research directions in the fabrication of highly efficient and stable PSCs, including key outcomes from our group. We begin by highlighting the critical challenges and their causes that are detrimental to the development of stable PSCs. We then discuss the fundamentals of halide perovskites including their optical and structural properties. This is followed by a description of the fabrication methods for perovskite crystals, films, and various device architectures. Next, we introduced target-oriented key strategies such as developing high-quality single crystals for redissolution as a perovskite precursor to fabricate phase-stable and reproducible PSCs, along with reduced material costs, employing multifunctional additives to get uniform, robust, and stable perovskite films, and interfacial engineering techniques for effective surface and buried interface defect passivation to improve charge transport and long-term stability. Finally, we conclude with a critical assessment and perspective on the future development of PSCs. This Account will provide valuable insights into the current state-of-the-art PSCs and promising strategies tailored to specific roles that can be combined to manipulate the perovskite structure for novel outcomes and further advancements.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"5 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542226","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Microenvironment Frontier for Electrochemical CO2 Conversion","authors":"Andrew B. Wong","doi":"10.1021/accountsmr.4c00294","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00294","url":null,"abstract":"low CO&lt;sub&gt;2&lt;/sub&gt; solubility in aqueous conditions the delicate balance between the delivery of essential proton donors for CO&lt;sub&gt;2&lt;/sub&gt;RR versus the strong tendency to convert donated protons to H&lt;sub&gt;2&lt;/sub&gt; via the competing hydrogen evolution reaction (HER) the delicate balance between reaction pathways toward multiple CO&lt;sub&gt;2&lt;/sub&gt;RR products dynamic changes in local pH, ion concentrations, hydrophobicity, and active sites in response to phenomena such as carbonate formation and restructuring of electrocatalysts Figure 1. Schematic overview of CO&lt;sub&gt;2&lt;/sub&gt;RR microenvironment effects. (a) Microenvironment impact on CO&lt;sub&gt;2&lt;/sub&gt;RR performance. (b) Microenvironment considerations: experimental conditions, electrocatalyst characteristics, and electrolyte characteristics. (c) Description of the activity and activity coefficient for CO&lt;sub&gt;2&lt;/sub&gt;, CO, and H&lt;sub&gt;2&lt;/sub&gt;O (or other proton donors). Activity is the lens through which to understand numerous phenomena within the CO&lt;sub&gt;2&lt;/sub&gt;RR microenvironment Figure 2. Schematic overview for macroscale, microscale, and nanoscale effects on planar (a–c) and porous (d–f) electrodes. First, the activity coefficient and concentration terms offer a helpful parameter space to compare the effects of various interventions and adjustments to the microenvironment that had previously been difficult to compare based on objective measures (Figure 1b). Second, this approach highlights the importance of improving our understanding of the relative contributions of three-phase (gas–liquid–solid) and larger area two-phase (liquid–solid) interfaces on CO&lt;sub&gt;2&lt;/sub&gt;RR, which has attracted recent attention. (12,13) Third, this understanding highlights the importance of developing new &lt;i&gt;in situ&lt;/i&gt; and &lt;i&gt;in operando&lt;/i&gt; analytical techniques to probe the local distributions of CO&lt;sub&gt;2&lt;/sub&gt;, CO, and H&lt;sub&gt;2&lt;/sub&gt;O under reaction conditions. Attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) has already shown promise for quantifying bound versus free water during CO&lt;sub&gt;2&lt;/sub&gt;RR. (13) What are strategies to extend recent fundamental developments on controlling water activity to improve CO&lt;sub&gt;2&lt;/sub&gt;RR performance at high current densities? How can we use the microenvironment to explore electrochemical strategies to simultaneously accomplish CO&lt;sub&gt;2&lt;/sub&gt; capture and conversion? Based on the historical development of CO&lt;sub&gt;2&lt;/sub&gt;RR approaches, can we or should we adopt new materials for CO&lt;sub&gt;2&lt;/sub&gt;RR GDLs and ionomers (typically materials developed for other chemical transformations with different requirements) to specialize in CO&lt;sub&gt;2&lt;/sub&gt;RR’s requirements? In CO&lt;sub&gt;2&lt;/sub&gt;RR, what is the structure of the three-phase gas–liquid–solid and other interfaces under reaction conditions? Leveraging the microenvironment, how can CO&lt;sub&gt;2&lt;/sub&gt; be used to make higher-value products or products that can integrate into the economy to achieve net negative CO&lt;sub&gt;2&lt;/sub&gt; ","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"16 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Extremely Downsized Materials: Ball-Milling-Enabled Universal Production and Size-Reduction-Induced Performance Enhancement","authors":"Ce Zhao, Liuyang Xiao, Zhexue Chen, Yong Zhang","doi":"10.1021/accountsmr.4c00306","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00306","url":null,"abstract":"Extremely downsized (including quantum-sized and subnanometer-sized) materials with sizes between atoms and nanoparticles have attracted tremendous attention thanks to their unique structures and exotic physical and chemical properties. Such unusual materials will induce a range of enhanced performances compared with their nanoscale and bulk counterparts, which can be beneficial to driving advancements of materials science as well as nanoscience and nanotechnology. However, it is quite challenging to prepare extremely downsized materials due to their ultrasmall sizes and ultralarge surfaces. Up to now, a variety of strategies have been explored for the preparation of extremely downsized materials, among which the basic categories are top-down and bottom-up methods. The former generally tailors bulk materials into downsized nanomaterials by physical routes, while the latter usually involves chemical (solution) processes to synthesize nanomaterials. During past decades, most efforts have been devoted to bottom-up methods for the synthesis of extremely downsized materials (e.g., colloidal quantum dots, sub-nanometer-sized materials, clusters, and supermolecules). Meanwhile, the production of extremely downsized materials through top-down methods is far from satisfactory, limited by their low manufacturing capacities and relatively expensive facilities. Note that nanomaterials produced by top-down physical methods exhibit entirely exposed surface/edge lattices, while the surface/edge lattices synthesized by bottom-up chemical methods are protected by ligands, making the surface/edge effects greatly obscured. Undoubtedly, exploiting a robust strategy to produce extremely downsized materials with maximized exposed lattices by all-physical top-down methods is required and desired. Our group has been focusing on all-physical production and extreme performances of extremely downsized materials since 2015. We have developed a universal and scalable strategy (i.e., the combination of silica-assisted ball-milling and sonication-assisted solvent exfoliation and treatment) for the all-physical production of quantum-sized materials. A series of quantum-sized materials with intrinsic characteristics have been produced, pushing forward the establishment of a complete database/library. Recently, two-stage silica-assisted ball-milling has been employed to realize the universal production of sub-nanometer-sized materials with entirely exposed and broken intrinsic lattices, suggesting that the top-down fabrication limit has reached the subnanometer (single-lattice) scale. Enhanced performances are demonstrated in both quantum-sized and sub-nanometer-sized materials because of their numerous broken lattices on surfaces/edges.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"135 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of Reaction System and Regulation of Catalyst Active Sites for Sustainable Ammonia Production","authors":"Zhe Meng, Miao-Miao Shi, Jun-Min Yan","doi":"10.1021/accountsmr.4c00103","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00103","url":null,"abstract":"Ammonia (NH₃) is widely used for human life and considered a green energy carrier without CO₂ emissions; thus, green and sustainable NH₃ synthesis is of great importance. The traditional Haber-Bosch process requires harsh conditions with serious environmental implications. Therefore, numerous research is focused on the efficient synthesis of NH₃ from abundant N₂/air and water under ambient conditions, utilizing renewable energy sources. Despite the fact that the electrocatalytic N₂ reduction reaction (eNRR) is an ideal method for NH₃ synthesis, the NH₃ yield and Faradaic efficiency (FE) are severally hampered by the inertness of N₂, impeding its industrial application. Various strategies have been proposed to synthesize highly efficient heterogeneous catalysts for N₂ adsorption and dissociation to improve NH₃ yield and FE. Besides, benefiting from the nonthermal plasma N₂ oxidation reaction (pNOR) and electrocatalytic nitrate/nitrite reduction reaction (eNO_<i>x</i>RR), the two-step approach overcomes the limitations of eNRR, attracting significant interest. This strategy facilitates N₂ splitting, which is a crucial step in the synthesis of NH₃. Additionally, eNO_<i>x</i>RR involves complex intermediates, making it essential to investigate catalysts with high selectivity of NH₃. Overall, through the optimization of catalysts and reaction systems, NH₃ can be synthesized with high efficiency. The two-step strategy is the most realistic process for mass NH₃ production, but several challenges still need to be addressed, including improving the overall energy efficiency and scaling up the technology for industrial applications.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"63 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}