Ayelet Tashakory, Sanjit Mondal, Venugopala Rao Battula, Gabriel Mark, Tirza Shmila, Michael Volokh, Menny Shalom
Polymeric carbon nitride (CN) has emerged as a promising photoanodic material in water-splitting photoelectrochemical cells (PEC). However, the current deposition methods of CN layers on substrates usually include a long heating process at 500−550 °C, which might cause sublimation or decomposition of the CN monomers and destruction of the substrate, leading to a nonuniform CN film. Herein, a simple, fast, and scalable energy-economic procedure to synthesize homogenous CN films is introduced. The predesigned CN monomers film is subjected for several minutes to higher temperatures than the standard calcination procedure. The short heating process allows the formation of a uniform CN layer, with excellent contact with the substrate and good activity as a photoanode in PEC. The optimal CN photoanode reaches photocurrent densities of ≈200 μA cm−2 at 1.23 versus reversible hydrogen electrode in neutral and acidic solutions and 120 μA cm−2 in a basic solution.
{"title":"Minute-Scale High-Temperature Synthesis of Polymeric Carbon Nitride Photoanodes","authors":"Ayelet Tashakory, Sanjit Mondal, Venugopala Rao Battula, Gabriel Mark, Tirza Shmila, Michael Volokh, Menny Shalom","doi":"10.1002/sstr.202400123","DOIUrl":"https://doi.org/10.1002/sstr.202400123","url":null,"abstract":"Polymeric carbon nitride (CN) has emerged as a promising photoanodic material in water-splitting photoelectrochemical cells (PEC). However, the current deposition methods of CN layers on substrates usually include a long heating process at 500−550 °C, which might cause sublimation or decomposition of the CN monomers and destruction of the substrate, leading to a nonuniform CN film. Herein, a simple, fast, and scalable energy-economic procedure to synthesize homogenous CN films is introduced. The predesigned CN monomers film is subjected for several minutes to higher temperatures than the standard calcination procedure. The short heating process allows the formation of a uniform CN layer, with excellent contact with the substrate and good activity as a photoanode in PEC. The optimal CN photoanode reaches photocurrent densities of ≈200 μA cm<sup>−2</sup> at 1.23 versus reversible hydrogen electrode in neutral and acidic solutions and 120 μA cm<sup>−2</sup> in a basic solution.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514524","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}
The evolution of flexible Zn-ion batteries (FZIBs) significantly hinges on the development of gel electrolytes, characterized by their mechanical properties, ionic conductivity, and environmentally friendly production processes. The prevailing challenge in this domain has been devising a gel electrolyte that encapsulates all these critical attributes effectively for practical application. This study presents a novel zinc ion gel (Zn-gel) electrolyte developed for FZIBs, synthesized via ethanol vapor-induced assembly of cellulose molecules. This innovative process fosters significant hydrogen bonding and ion-complexation with Zn2+ ions, resulting in a gel with exceptional mechanical strength (0.88 MPa), high ion transference (over 0.7), and impressive ionic conductivity (8.39 mS cm−1). The Zn-gel enables a FZIB to achieve a reversible capacity of 207.3 mAh g−1 and over 93% Coulombic efficiency after 500 cycles, devoid of liquid electrolyte. Highlighting a promising route for high-performance, eco-friendly gel electrolytes, this research advances flexible electronics and portable device applications, demonstrating the profound potential of bio-based polymers in enhancing energy storage technology.
柔性锌离子电池（FZIB）的发展在很大程度上取决于凝胶电解质的开发，凝胶电解质具有机械性能、离子导电性和环保生产工艺等特点。这一领域面临的主要挑战是设计出一种凝胶电解质，它能有效封装所有这些关键属性，以实现实际应用。本研究介绍了一种为 FZIB 开发的新型锌离子凝胶（Zn-gel）电解质，它是通过乙醇蒸汽诱导纤维素分子组装合成的。这种创新工艺促进了与 Zn2+ 离子的氢键和离子络合，从而使凝胶具有超强的机械强度（0.88 兆帕）、高离子转移率（超过 0.7）和惊人的离子电导率（8.39 mS cm-1）。在不使用液态电解质的情况下，锌凝胶使 FZIB 在 500 次循环后达到 207.3 mAh g-1 的可逆容量和 93% 以上的库仑效率。这项研究为高性能、环保型凝胶电解质开辟了一条前景广阔的途径，推动了柔性电子器件和便携式设备的应用，展示了生物基聚合物在提高储能技术方面的巨大潜力。
{"title":"Ethanol Vapor-Induced Synthesis of Robust, High-Efficiency Zinc Ion Gel Electrolytes for Flexible Zn-Ion Batteries","authors":"Zihao Zheng, Wanke Cheng, Geyuan Jiang, Xiaona Li, Jinsong Sun, Ying Zhu, Dawei Zhao, Haipeng Yu","doi":"10.1002/sstr.202400180","DOIUrl":"https://doi.org/10.1002/sstr.202400180","url":null,"abstract":"The evolution of flexible Zn-ion batteries (FZIBs) significantly hinges on the development of gel electrolytes, characterized by their mechanical properties, ionic conductivity, and environmentally friendly production processes. The prevailing challenge in this domain has been devising a gel electrolyte that encapsulates all these critical attributes effectively for practical application. This study presents a novel zinc ion gel (Zn-gel) electrolyte developed for FZIBs, synthesized via ethanol vapor-induced assembly of cellulose molecules. This innovative process fosters significant hydrogen bonding and ion-complexation with Zn<sup>2+</sup> ions, resulting in a gel with exceptional mechanical strength (0.88 MPa), high ion transference (over 0.7), and impressive ionic conductivity (8.39 mS cm<sup>−1</sup>). The Zn-gel enables a FZIB to achieve a reversible capacity of 207.3 mAh g<sup>−1</sup> and over 93% Coulombic efficiency after 500 cycles, devoid of liquid electrolyte. Highlighting a promising route for high-performance, eco-friendly gel electrolytes, this research advances flexible electronics and portable device applications, demonstrating the profound potential of bio-based polymers in enhancing energy storage technology.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514526","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}
Current advances in synthesizing and characterizing atomically precise monodisperse metal clusters (AMCs) at the subnanometer scale have opened up new possibilities in quantum materials research. Their quantizied “molecule-like” electronic structure showcases unique stability, and physical and chemical properties differentiate them from larger nanoparticles. When integrated into inorganic materials that interact with the environment and sunlight, AMCs serve to enhance their (photo)catalytic activity and optoelectronic properties. Their tiny size makes AMCs isolated in the gas phase amenable to atom-scale modeling using either density functional theory (DFT) or methods at a high level of ab initio theory, even addressing nonadiabatic (e.g., Jahn–Teller) effects. Surface-supported AMCs can be routinely modeled using DFT, enabling long real-time molecular dynamics simulations. Their optical properties can also be addressed using time-dependent DFT or reduced density matrix (RDM) theory. These theoretical–computational efforts aim to achieve predictability and molecular-level understanding of the stability and properties of AMCs as function of their composition, size, and structural fluxionality in different thermodynamical conditions (temperature and pressure). In this perspective, the potential of ab initio and DFT-based modeling is illustrated through recent studies of unsupported and surface-supported AMCs. Future directions of research are also discussed, including applications and methodological enhancements beyond the state-of-the-art.
目前在亚纳米尺度合成和表征原子精确单分散金属团簇（AMC）方面取得的进展为量子材料研究开辟了新的可能性。它们量子化的 "分子状 "电子结构显示出独特的稳定性，其物理和化学特性也有别于较大的纳米颗粒。当将 AMC 集成到与环境和阳光相互作用的无机材料中时，AMC 可增强其（光）催化活性和光电特性。由于 AMC 的尺寸极小，因此可以使用密度泛函理论（DFT）或高水平的 ab initio 理论方法，甚至是非绝热（如 Jahn-Teller）效应，对分离在气相中的 AMC 进行原子尺度建模。表面支持的 AMC 可以使用 DFT 进行常规建模，从而实现长时间的实时分子动力学模拟。它们的光学特性也可以使用随时间变化的 DFT 或还原密度矩阵 (RDM) 理论来解决。这些理论计算工作旨在实现对 AMC 在不同热力学条件（温度和压力）下的稳定性和特性的可预测性和分子级理解，这些特性是其组成、尺寸和结构通性的函数。从这个角度出发，通过对无支撑和表面支撑 AMC 的最新研究，说明了基于 ab initio 和 DFT 的建模潜力。此外，还讨论了未来的研究方向，包括最新技术之外的应用和方法改进。
{"title":"An Ab Initio Journey toward the Molecular-Level Understanding and Predictability of Subnanometric Metal Clusters","authors":"María Pilar de Lara-Castells","doi":"10.1002/sstr.202400147","DOIUrl":"https://doi.org/10.1002/sstr.202400147","url":null,"abstract":"Current advances in synthesizing and characterizing atomically precise monodisperse metal clusters (AMCs) at the subnanometer scale have opened up new possibilities in quantum materials research. Their quantizied “molecule-like” electronic structure showcases unique stability, and physical and chemical properties differentiate them from larger nanoparticles. When integrated into inorganic materials that interact with the environment and sunlight, AMCs serve to enhance their (photo)catalytic activity and optoelectronic properties. Their tiny size makes AMCs isolated in the gas phase amenable to atom-scale modeling using either density functional theory (DFT) or methods at a high level of <i>ab initio</i> theory, even addressing nonadiabatic (e.g., Jahn–Teller) effects. Surface-supported AMCs can be routinely modeled using DFT, enabling long real-time molecular dynamics simulations. Their optical properties can also be addressed using time-dependent DFT or reduced density matrix (RDM) theory. These theoretical–computational efforts aim to achieve predictability and molecular-level understanding of the stability and properties of AMCs as function of their composition, size, and structural fluxionality in different thermodynamical conditions (temperature and pressure). In this perspective, the potential of <i>ab initio</i> and DFT-based modeling is illustrated through recent studies of unsupported and surface-supported AMCs. Future directions of research are also discussed, including applications and methodological enhancements beyond the state-of-the-art.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514426","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}
High-entropy alloys (HEAs) are novel materials composed of multiple elements with nearly equal concentrations and they exhibit exceptional properties such as high strength, ductility, thermal stability, and corrosion resistance. However, the intricate and diverse structures of HEAs pose significant challenges to understanding and predicting their behavior at different length scales. This review summarizes recent advances in computational simulations and experiments of structure-property relationships in HEAs at the nano/micro scales. Various methods such as first-principles calculations, molecular dynamics simulations, phase diagram calculations, and finite element simulations are discussed for revealing atomic/chemical and crystal structures, defect formation and migration, diffusion and phase transition, phase formation and stability, stress-strain distribution, deformation behavior, and thermodynamic properties of HEAs. Emphasis is placed on the synergistic effects of computational simulations and experiments in terms of validation and complementarity to provide insights into the underlying mechanisms and evolutionary rules of HEAs. Additionally, current challenges and future directions for computational and experimental studies of HEAs are identified, including accuracy, efficiency, and scalability of methods, integration of multiscale and multiphysics models, and exploration of practical applications of HEAs.
高熵合金（HEAs）是一种新型材料，由浓度几乎相等的多种元素组成，具有高强度、延展性、热稳定性和耐腐蚀性等优异性能。然而，HEAs 复杂多样的结构给理解和预测其在不同长度尺度上的行为带来了巨大挑战。本综述总结了在纳米/微米尺度上对 HEAs 结构-性能关系进行计算模拟和实验的最新进展。文章讨论了第一原理计算、分子动力学模拟、相图计算和有限元模拟等各种方法，以揭示 HEAs 的原子/化学和晶体结构、缺陷形成和迁移、扩散和相变、相形成和稳定性、应力应变分布、变形行为和热力学性质。重点是计算模拟和实验在验证和互补方面的协同作用，以便深入了解 HEAs 的内在机制和演化规律。此外，还确定了 HEA 计算和实验研究的当前挑战和未来方向，包括方法的准确性、效率和可扩展性，多尺度和多物理模型的集成，以及 HEA 的实际应用探索。
{"title":"Accelerating the Exploration of High-Entropy Alloys: Synergistic Effects of Integrating Computational Simulation and Experiments","authors":"Deyu Jiang, Yuhua Li, Liqiang Wang, Lai-Chang Zhang","doi":"10.1002/sstr.202400110","DOIUrl":"https://doi.org/10.1002/sstr.202400110","url":null,"abstract":"High-entropy alloys (HEAs) are novel materials composed of multiple elements with nearly equal concentrations and they exhibit exceptional properties such as high strength, ductility, thermal stability, and corrosion resistance. However, the intricate and diverse structures of HEAs pose significant challenges to understanding and predicting their behavior at different length scales. This review summarizes recent advances in computational simulations and experiments of structure-property relationships in HEAs at the nano/micro scales. Various methods such as first-principles calculations, molecular dynamics simulations, phase diagram calculations, and finite element simulations are discussed for revealing atomic/chemical and crystal structures, defect formation and migration, diffusion and phase transition, phase formation and stability, stress-strain distribution, deformation behavior, and thermodynamic properties of HEAs. Emphasis is placed on the synergistic effects of computational simulations and experiments in terms of validation and complementarity to provide insights into the underlying mechanisms and evolutionary rules of HEAs. Additionally, current challenges and future directions for computational and experimental studies of HEAs are identified, including accuracy, efficiency, and scalability of methods, integration of multiscale and multiphysics models, and exploration of practical applications of HEAs.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530588","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}
Francois-Marie Allioux, Sahar Nazari, Mohammad B. Ghasemian, Ali Zavabeti, Zengxia Pei, Josh Leverett, Somayeh Rafiezadeh, Amar K. Salih, Curtis P. Irvine, Mahroo Baharfar, Laetitia Bardet, Moonika S. Widjajana, Yuan Chi, Dorna Esrafilzadeh, Ali R. Jalili, Nima Haghdadi, Jianbo Tang, Kevin J. Laws, Cuong Ton-That, Torben Daeneke, Rahman Daiyan, Md Arifur Rahim, Kourosh Kalantar-Zadeh
Gallium-based liquid metal alloys exhibit unconventional and intriguing properties as metallic solvents, demonstrating an exceptional potential to dissolve and reconfigure a vast array of elements within the liquid metal matrix. Leveraging on these distinctive characteristics of gallium-based alloys, the synthesis of high-entropy liquid metal alloys (HELMAs) in low dimensions is reported. The nanoscale HELMAs offer advantages including the solvation of multiple metallic elements at room temperature, while promoting their atomic dispersion at elevated concentrations. Entropy estimations for HELMAs surpass those of high-temperature molten metals, leading to the realization of high-entropy liquid metal systems at room temperature. Through a proof-of-concept hydrogen evolution reaction comparison, the potential of these HELMAs in enhancing the activities of nanocatalysts is demonstrated. In this case, atomic dispersion of Pt is shown in senary GaIn-AuCuPtPd HELMA, contrasting with lower entropy systems in which Pt forms discernible clusters. These presented features can lead to catalytic systems with enhanced and tailored activities.
{"title":"Atomic Dispersion via High-Entropy Liquid Metal Alloys","authors":"Francois-Marie Allioux, Sahar Nazari, Mohammad B. Ghasemian, Ali Zavabeti, Zengxia Pei, Josh Leverett, Somayeh Rafiezadeh, Amar K. Salih, Curtis P. Irvine, Mahroo Baharfar, Laetitia Bardet, Moonika S. Widjajana, Yuan Chi, Dorna Esrafilzadeh, Ali R. Jalili, Nima Haghdadi, Jianbo Tang, Kevin J. Laws, Cuong Ton-That, Torben Daeneke, Rahman Daiyan, Md Arifur Rahim, Kourosh Kalantar-Zadeh","doi":"10.1002/sstr.202400294","DOIUrl":"https://doi.org/10.1002/sstr.202400294","url":null,"abstract":"Gallium-based liquid metal alloys exhibit unconventional and intriguing properties as metallic solvents, demonstrating an exceptional potential to dissolve and reconfigure a vast array of elements within the liquid metal matrix. Leveraging on these distinctive characteristics of gallium-based alloys, the synthesis of high-entropy liquid metal alloys (HELMAs) in low dimensions is reported. The nanoscale HELMAs offer advantages including the solvation of multiple metallic elements at room temperature, while promoting their atomic dispersion at elevated concentrations. Entropy estimations for HELMAs surpass those of high-temperature molten metals, leading to the realization of high-entropy liquid metal systems at room temperature. Through a proof-of-concept hydrogen evolution reaction comparison, the potential of these HELMAs in enhancing the activities of nanocatalysts is demonstrated. In this case, atomic dispersion of Pt is shown in senary GaIn-AuCuPtPd HELMA, contrasting with lower entropy systems in which Pt forms discernible clusters. These presented features can lead to catalytic systems with enhanced and tailored activities.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514424","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}
Beatriz Merillas, Carlos A. García-González, Tomás Enrique Gómez Álvarez-Arenas, Miguel Ángel Rodríguez-Pérez
The aerogel performance for industrial uses can be tailored using several chemical and physical strategies. The effects of a controlled densification on polyurethane aerogels are herein studied by analyzing their textural, mechanical, sound, optical, and thermal insulating properties. The produced aerogels are uniaxially compressed to different strains (30%–80%) analyzing the consequent changes in the structures and, therefore, final properties. As expected, their mechanical stiffness can be significantly increased by compression (until 55-fold higher elastic modulus for 80%-strain), while the light transmittance does not noticeably worsen until it is compressed more than 60%. Additionally, the modifications produced in the heat transfer contributions are analyzed, obtaining the optimum balance between density increase and pore size reduction. The minimum thermal conductivity (14.5%-reduction) is obtained by compressing the aerogel to 50%-strain, where the increment in the solid conduction is surpassed by the reduction of the radiative and gas contributions. This strategy avoids tedious chemical modifications in the synthesis procedure to control the final structure of the aerogels, leading to the possibility of carefully adapting their structure and properties through a simple method such as densification. Thus, it allows to obtain aerogels for current and on-demand applications, which is one of the main challenges in the field.
{"title":"Towards the Optimization of Polyurethane Aerogel Properties by Densification: Exploring the Structure–Properties Relationship","authors":"Beatriz Merillas, Carlos A. García-González, Tomás Enrique Gómez Álvarez-Arenas, Miguel Ángel Rodríguez-Pérez","doi":"10.1002/sstr.202400120","DOIUrl":"https://doi.org/10.1002/sstr.202400120","url":null,"abstract":"The aerogel performance for industrial uses can be tailored using several chemical and physical strategies. The effects of a controlled densification on polyurethane aerogels are herein studied by analyzing their textural, mechanical, sound, optical, and thermal insulating properties. The produced aerogels are uniaxially compressed to different strains (30%–80%) analyzing the consequent changes in the structures and, therefore, final properties. As expected, their mechanical stiffness can be significantly increased by compression (until 55-fold higher elastic modulus for 80%-strain), while the light transmittance does not noticeably worsen until it is compressed more than 60%. Additionally, the modifications produced in the heat transfer contributions are analyzed, obtaining the optimum balance between density increase and pore size reduction. The minimum thermal conductivity (14.5%-reduction) is obtained by compressing the aerogel to 50%-strain, where the increment in the solid conduction is surpassed by the reduction of the radiative and gas contributions. This strategy avoids tedious chemical modifications in the synthesis procedure to control the final structure of the aerogels, leading to the possibility of carefully adapting their structure and properties through a simple method such as densification. Thus, it allows to obtain aerogels for current and on-demand applications, which is one of the main challenges in the field.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514425","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}
Green and highly selective synthesis of ammonia (NH3) via electrochemical reduction reaction of toxic nitrite (NO2−RR) in a neutral electrolyte is a feasible solution for energy and environmental issues. Dual-nature electrocatalysts combining metal and metal-derived materials are crucial for enhancing the selectivity parameter and efficacy of this reaction. Here, Pd-, Pt-, Ru-, and Ir-decorated Co3(PO4)2 (CoPi) composites with a robust metal–support interaction are obtained via the one-pot pulsed laser ablation in liquid method. Among the designed composites, Ir–CoPi affords ≈100% Faradaic efficiency, mass balance, and selectivity toward NH3 product at sufficiently low potentials. Further, it affords the highest NH3 yield rate of 19.13 mg h−1 cm−2 with 78.1% removal of toxic NO2− with a rate constant kapp = 0.31 mm min−1 under −1.6 V versus Ag/AgCl. In situ experiments and theoretical investigations reveal the underlying mechanisms responsible for this outstanding performance of Ir–CoPi, which can be accredited to the generation of specific active sites on the Ir component. Insights derived from the evolving intermediate reactive species provide new opportunities for large-scale NH3 production through electrochemical techniques, density functional theory calculations, and the improvement of the corresponding industrial processes.
{"title":"Pulsed Laser-Initiated Dual-Catalytic Interfaces for Directed Electroreduction of Nitrite to Ammonia","authors":"Talshyn Begildayeva, Jayaraman Theerthagiri, Vy Thuy Nguyen, Ahreum Min, Hyeyoung Shin, Myong Yong Choi","doi":"10.1002/sstr.202400187","DOIUrl":"https://doi.org/10.1002/sstr.202400187","url":null,"abstract":"Green and highly selective synthesis of ammonia (NH<sub>3</sub>) via electrochemical reduction reaction of toxic nitrite (NO<sub>2</sub><sup>−</sup>RR) in a neutral electrolyte is a feasible solution for energy and environmental issues. Dual-nature electrocatalysts combining metal and metal-derived materials are crucial for enhancing the selectivity parameter and efficacy of this reaction. Here, Pd-, Pt-, Ru-, and Ir-decorated Co<sub>3</sub>(PO<sub>4</sub>)<sub>2</sub> (CoPi) composites with a robust metal–support interaction are obtained via the one-pot pulsed laser ablation in liquid method. Among the designed composites, Ir–CoPi affords ≈100% Faradaic efficiency, mass balance, and selectivity toward NH<sub>3</sub> product at sufficiently low potentials. Further, it affords the highest NH<sub>3</sub> yield rate of 19.13 mg h<sup>−1</sup> cm<sup>−2</sup> with 78.1% removal of toxic NO<sub>2</sub><sup>−</sup> with a rate constant <i>k</i><sub>app</sub> = 0.31 m<span>m</span> min<sup>−1</sup> under −1.6 V versus Ag/AgCl. In situ experiments and theoretical investigations reveal the underlying mechanisms responsible for this outstanding performance of Ir–CoPi, which can be accredited to the generation of specific active sites on the Ir component. Insights derived from the evolving intermediate reactive species provide new opportunities for large-scale NH<sub>3</sub> production through electrochemical techniques, density functional theory calculations, and the improvement of the corresponding industrial processes.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514525","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}
Heebae Kim, Eunbin Jang, Jinil Cho, Seonmi Pyo, Heejun Yun, Jeewon Lee, Byeongyun Min, Juyeon Han, Jeeyoung Yoo, Youn Sang Kim
All-solid-state Li-metal battery (ASSLB) represents advantageous energy storage system for automotive applications. For ASSLB, inorganic solid electrolyte is essential in determining safety and cycling performance. However, significant challenges persist in practical construction of ASSLB with optimized electrolyte. Specifically, electrolyte's structural instability influencing its electrochemical performance remains critical issue within typical operating temperatures for ASSLB in electric vehicles. Herein, this challenge is fundamentally addressed by substituting trace amount of lithium with cadmium, which lacks crystal field stabilization energy. This strategy of atomic interaction modification has induced electrolyte's structural distortion and electronic alteration by deliberately introducing disorder at local lithium sites. Li symmetric cell with cadmium-substituted antiperovskite solid electrolyte exhibits outstanding critical current density of 11.5 mA cm−2 (5.75 mAh cm−2) and excellent stability for 3000 h at 10.0 mA cm−2 (5.0 mAh cm−2). This study highlights explicit research direction for breakthrough of ASSLB, focusing on understanding how local distortion affects complex inorganic materials.
全固态锂金属电池（ASSLB）是汽车应用中的优势储能系统。对于全固态锂金属电池而言，无机固体电解质对其安全性和循环性能至关重要。然而，在实际建造具有优化电解质的 ASSLB 时，仍然面临着巨大的挑战。具体来说，电解质的结构不稳定性会影响其电化学性能，这在电动汽车 ASSLB 的典型工作温度下仍是一个关键问题。在这里，通过用缺乏晶体场稳定能量的镉替代微量锂，从根本上解决了这一难题。这种原子相互作用修饰策略通过故意在局部锂位点引入无序状态，诱发电解质结构畸变和电子变化。使用镉取代的反包晶石固体电解质的锂对称电池表现出卓越的临界电流密度，达到 11.5 mA cm-2（5.75 mAh cm-2），并在 10.0 mA cm-2（5.0 mAh cm-2）的条件下保持了 3000 小时的卓越稳定性。这项研究强调了突破 ASSLB 的明确研究方向，重点是了解局部变形如何影响复杂的无机材料。
{"title":"Strategic Atomic Interaction Modification for Highly Durable Inorganic Solid Electrolytes in Advanced All-Solid-State Li-Metal Batteries","authors":"Heebae Kim, Eunbin Jang, Jinil Cho, Seonmi Pyo, Heejun Yun, Jeewon Lee, Byeongyun Min, Juyeon Han, Jeeyoung Yoo, Youn Sang Kim","doi":"10.1002/sstr.202400091","DOIUrl":"https://doi.org/10.1002/sstr.202400091","url":null,"abstract":"All-solid-state Li-metal battery (ASSLB) represents advantageous energy storage system for automotive applications. For ASSLB, inorganic solid electrolyte is essential in determining safety and cycling performance. However, significant challenges persist in practical construction of ASSLB with optimized electrolyte. Specifically, electrolyte's structural instability influencing its electrochemical performance remains critical issue within typical operating temperatures for ASSLB in electric vehicles. Herein, this challenge is fundamentally addressed by substituting trace amount of lithium with cadmium, which lacks crystal field stabilization energy. This strategy of atomic interaction modification has induced electrolyte's structural distortion and electronic alteration by deliberately introducing disorder at local lithium sites. Li symmetric cell with cadmium-substituted antiperovskite solid electrolyte exhibits outstanding critical current density of 11.5 mA cm<sup>−2</sup> (5.75 mAh cm<sup>−2</sup>) and excellent stability for 3000 h at 10.0 mA cm<sup>−2</sup> (5.0 mAh cm<sup>−2</sup>). This study highlights explicit research direction for breakthrough of ASSLB, focusing on understanding how local distortion affects complex inorganic materials.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141552072","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}
Piers Coia, Bhagya Dharmasiri, David J. Hayne, Ameya Borkar, Carol Hua, Elmer Austria, Behnam Akhavan, Mia Angela Nuñeza Judicpa, Ken Aldren Sumaya Usman, Joselito Razal, Luke C. Henderson
The multifunctionality of carbon fiber (CF) is being extensively explored. Herein, polyimide covalent organic frameworks (PI-COFs) are grafted bound to CF to enhance their mechanical and electrochemical properties. Here, a range of COF scaffolds are grafted to the surface of CFs via a two-step functionalization. First, melamine is tethered to the fiber surface to provide an anchoring point for the COFs followed by a “graft from” approach to grow three different sized PI-COFs utilizing three differently sized dianhydride, PMDA to form MA-PMDA, NTCDA to form MA-NTCDA, and PTCDA to form MA-PTCDA COFs. These COFs increase the capacitance of CF by a maximum of 2.9 F g−1 (480% increase) for the MA-PTCDA, this coincides with an increase in interfacial shear strength by 67.5% and 52% for MA-NTCDA and MA-PTCDA, respectively. This data represents that the first-time CF has been modified with PI-COFs and allows access to COF properties including their porosity and CO2 capture ability while being attached to a substrate. This may lead to additional high-value recyclability and second-life applications for CFs.
{"title":"Hierarchical Polyimide-Covalent Organic Frameworks Carbon Fiber Structures Enhancing Physical and Electrochemical Properties","authors":"Piers Coia, Bhagya Dharmasiri, David J. Hayne, Ameya Borkar, Carol Hua, Elmer Austria, Behnam Akhavan, Mia Angela Nuñeza Judicpa, Ken Aldren Sumaya Usman, Joselito Razal, Luke C. Henderson","doi":"10.1002/sstr.202400166","DOIUrl":"https://doi.org/10.1002/sstr.202400166","url":null,"abstract":"The multifunctionality of carbon fiber (CF) is being extensively explored. Herein, polyimide covalent organic frameworks (PI-COFs) are grafted bound to CF to enhance their mechanical and electrochemical properties. Here, a range of COF scaffolds are grafted to the surface of CFs via a two-step functionalization. First, melamine is tethered to the fiber surface to provide an anchoring point for the COFs followed by a “graft from” approach to grow three different sized PI-COFs utilizing three differently sized dianhydride, PMDA to form <b>MA-PMDA</b>, NTCDA to form <b>MA-NTCDA,</b> and PTCDA to form <b>MA-PTCDA</b> COFs. These COFs increase the capacitance of CF by a maximum of 2.9 F g<sup>−1</sup> (480% increase) for the <b>MA-PTCDA</b>, this coincides with an increase in interfacial shear strength by 67.5% and 52% for <b>MA-NTCDA</b> and <b>MA-PTCDA,</b> respectively. This data represents that the first-time CF has been modified with PI-COFs and allows access to COF properties including their porosity and CO<sub>2</sub> capture ability while being attached to a substrate. This may lead to additional high-value recyclability and second-life applications for CFs.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141514427","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}
The edge reconstruction of two-dimensional (2D) materials is significant for the stability, properties, and applications. Significant progress has been made in understanding the edge reconstruction of 2D materials. Herein, an overview of the latest theoretical and experimental advances on edge reconstruction of α-phase phosphorene nanoribbon and IV–VI group binary compounds MX (M = Ge, Sn; X = S, Se), focusing on the mechanism, stability, physical, and chemical properties of the edge reconstructions is provided. The status, challenges, and contradictions in experiments and theory are addressed and the progress in edge reconstruction of α-phase puckered 2D materials as well as the effects of edge reconstruction on physicochemical properties are systematically introduced. A novel tube-like edge reconstruction is suggested to be universal for α-phase puckered monolayers. While ZZ(U) edge can be another important reconstruction in bilayer. Beyond the review, the edge structures of phosphorene have odd–even layered oscillations are also proposed. The edge terminations can affect the exfoliation mechanism and electronic, transport properties. Interesting, unique U-edge, which has been verified by experiment, exhibits nearly edgeless electronic and thermal transport, which is beneficial for ultrafast microelectronics.
{"title":"The Unique Edge Reconstructions and Related Edgeless Properties of Mono- and Few-Layered α-Phase Puckered 2D Materials","authors":"Mingyue Xia, Yuan Chang, Zhigen Yu, Hongsheng Liu, Si Zhou, Jijun Zhao, Junfeng Gao","doi":"10.1002/sstr.202400191","DOIUrl":"https://doi.org/10.1002/sstr.202400191","url":null,"abstract":"The edge reconstruction of two-dimensional (2D) materials is significant for the stability, properties, and applications. Significant progress has been made in understanding the edge reconstruction of 2D materials. Herein, an overview of the latest theoretical and experimental advances on edge reconstruction of <i>α</i>-phase phosphorene nanoribbon and IV–VI group binary compounds MX (M = Ge, Sn; X = S, Se), focusing on the mechanism, stability, physical, and chemical properties of the edge reconstructions is provided. The status, challenges, and contradictions in experiments and theory are addressed and the progress in edge reconstruction of <i>α</i>-phase puckered 2D materials as well as the effects of edge reconstruction on physicochemical properties are systematically introduced. A novel tube-like edge reconstruction is suggested to be universal for <i>α</i>-phase puckered monolayers. While ZZ(U) edge can be another important reconstruction in bilayer. Beyond the review, the edge structures of phosphorene have odd–even layered oscillations are also proposed. The edge terminations can affect the exfoliation mechanism and electronic, transport properties. Interesting, unique U-edge, which has been verified by experiment, exhibits nearly edgeless electronic and thermal transport, which is beneficial for ultrafast microelectronics.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141552068","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}
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