Accounts of materials research最新文献

{"title":"Perspectives of Flexible Thermoelectric Fibers by Thermal Drawing Techniques","authors":"Pengyu Zhang,  and , Ting Zhang*, ","doi":"10.1021/accountsmr.4c0034310.1021/accountsmr.4c00343","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00343https://doi.org/10.1021/accountsmr.4c00343","url":null,"abstract":"<p >Wearable devices are increasingly being used to prevent diseases and to enhance physical health. However, this advancement comes with the challenge of high power consumption. Existing portable power storage or generation solutions often fail to meet the requirements for uninterrupted power supply, compact size, light weight, and low noise. Thermoelectric materials have emerged as a promising solution for portable energy supplies due to their ability to directly convert body heat into electricity. These materials not only provide clean energy for wearable devices but also support solid-state refrigeration, temperature sensing, and monitoring functions. Nevertheless, conventional inorganic materials with high thermoelectric properties face several challenges, such as brittleness, poor postprocessing capabilities, large size, complex preparation procedures, and high cost, limiting their suitability for heat sources with irregular surfaces. Conversely, while organic thermoelectric materials are more flexible, they exhibit weak thermoelectric performance and cannot meet the growing power demands of modern wearable devices. Recently, through thermal drawing technology, high-performance inorganic materials can be fabricated into flexible thermoelectric fibers, combining excellent thermoelectric properties with flexibility. These fibers are capable of harvesting waste heat to generate electricity, assisting in body temperature regulation, and measuring the temperature of irregular heat sources, thereby meeting the requirements of wearable devices. Wearable fabric devices woven from inorganic thermoelectric fibers retain the thermoelectric efficiency of bulk inorganic materials while offering additional benefits such as washability, fatigue resistance, portability, and the potential for large-scale and low-cost production. These advantages enable wearable thermoelectric devices to operate effectively in diverse and challenging environments. However, current commercial equipment is difficult to accurately measure micrometer/nanometer-scale fiber thermoelectric fibers. Herein, we have developed an in situ measurement system for the thermoelectric properties of micro/nanoscale materials, which can perform integrated in situ testing of the electrical conductivity, Seebeck coefficient, and thermal conductivity of thermoelectric fibers, reducing the measurement uncertainty compared to measuring multiple parameters for multiple samples separately.</p><p >This Account primarily summarizes our efforts to enhance the performance of flexible thermoelectric fibers produced by the thermal drawing technique and demonstrates the practical applications of these materials. By preparing fibrous inorganic materials with varying elemental compositions and microstructures and developing an in situ measurement system for characterizing thermoelectric properties of micro/nanoscale fiber materials, we have investigated and analyzed fibers with diverse thermoelectric properti","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 3","pages":"306–315 306–315"},"PeriodicalIF":14.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143714078","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":"Perspectives of Flexible Thermoelectric Fibers by Thermal Drawing Techniques","authors":"Pengyu Zhang, Ting Zhang","doi":"10.1021/accountsmr.4c00343","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00343","url":null,"abstract":"Wearable devices are increasingly being used to prevent diseases and to enhance physical health. However, this advancement comes with the challenge of high power consumption. Existing portable power storage or generation solutions often fail to meet the requirements for uninterrupted power supply, compact size, light weight, and low noise. Thermoelectric materials have emerged as a promising solution for portable energy supplies due to their ability to directly convert body heat into electricity. These materials not only provide clean energy for wearable devices but also support solid-state refrigeration, temperature sensing, and monitoring functions. Nevertheless, conventional inorganic materials with high thermoelectric properties face several challenges, such as brittleness, poor postprocessing capabilities, large size, complex preparation procedures, and high cost, limiting their suitability for heat sources with irregular surfaces. Conversely, while organic thermoelectric materials are more flexible, they exhibit weak thermoelectric performance and cannot meet the growing power demands of modern wearable devices. Recently, through thermal drawing technology, high-performance inorganic materials can be fabricated into flexible thermoelectric fibers, combining excellent thermoelectric properties with flexibility. These fibers are capable of harvesting waste heat to generate electricity, assisting in body temperature regulation, and measuring the temperature of irregular heat sources, thereby meeting the requirements of wearable devices. Wearable fabric devices woven from inorganic thermoelectric fibers retain the thermoelectric efficiency of bulk inorganic materials while offering additional benefits such as washability, fatigue resistance, portability, and the potential for large-scale and low-cost production. These advantages enable wearable thermoelectric devices to operate effectively in diverse and challenging environments. However, current commercial equipment is difficult to accurately measure micrometer/nanometer-scale fiber thermoelectric fibers. Herein, we have developed an in situ measurement system for the thermoelectric properties of micro/nanoscale materials, which can perform integrated in situ testing of the electrical conductivity, Seebeck coefficient, and thermal conductivity of thermoelectric fibers, reducing the measurement uncertainty compared to measuring multiple parameters for multiple samples separately.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"8 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084134","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":"Thermoresponsive Hydrogels for the Construction of Smart Windows, Sensors, and Actuators","authors":"Keunhyuk Ryu, Gang Li, Keyi Zhang, Jianguo Guan*, Yi Long* and ZhiLi Dong*, ","doi":"10.1021/accountsmr.5c0000710.1021/accountsmr.5c00007","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00007https://doi.org/10.1021/accountsmr.5c00007","url":null,"abstract":"<p >Thermoresponsive hydrogels possess an inherent capacity for autonomous adjustment of their properties in response to temperature variations, eliminating the requirement for external power sources and rendering them suitable for diverse environmental applications. Our discourse commences by establishing a foundational comprehension of the two principal categories governing thermal transitions in thermoresponsive hydrogels, namely, the Lower Critical Solution Temperature (LCST) and the Upper Critical Solution Temperature (UCST). These thermal transitions, LCST and UCST, are pivotal determinants of the physical characteristics and reactivity of hydrogels, as they regulate the response and deformations of temperature-sensitive hydrogels across varying environmental conditions. Moreover, the integration of these hydrogels within the photonic crystal (PC) structures has emerged as a notable approach to modulating dielectric constants or lattice configurations, leading to color change. Due to these remarkable properties, thermoresponsive hydrogels have garnered significant research attention for various smart material applications, including energy-saving technologies, environmental and biometric sensing, and control systems. Despite these distinctive features driving extensive research in smart materials areas, challenges persist due to the inherent water-rich composition and compromised mechanical integrity of hydrogels. These limitations impede their deployment in extreme temperature conditions and make them susceptible to mechanical stress. To address these challenges, innovative strategies, including entanglement-induced reinforcement, incorporation of antifreeze agents, and the application of polyvalent metal ions, have been devised to bolster mechanical robustness and enhance the desired performance metrics of hydrogels.</p><p >This Account provides readers with comprehensive insights into recent advancements in the field of thermoresponsive hydrogels, with a primary focus on classifying hydrogel categories and elucidating innovative fabrication techniques, particularly with reference to research conducted by our research groups. We systematically expound upon the underlying principles that govern reactions contingent upon thermal transition categories, underscored by illustrative examples of representative hydrogels and the synthetic methodologies employed. Following this, we conduct a comprehensive review of recent innovative property enhancement strategies aimed at broadening the applicability and utility in practical contexts of thermoresponsive hydrogel, addressing existing challenges such as drying, freezing, mechanical properties, and durability. Subsequently, an extensive analysis of applications stemming from the realm of thermoresponsive hydrogels is undertaken with a focus on the latest research trends and accomplishments pertaining to the innovative utilization of these materials in domains such as smart windows, actuators, and se","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 3","pages":"379–392 379–392"},"PeriodicalIF":14.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/accountsmr.5c00007","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143714079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Block Copolymer Based Porous Carbon Fiber─Synthesis, Processing, and Applications","authors":"Adeel Zia, Yue Zhang, Akshara Paras Parekh and Guoliang Liu*, ","doi":"10.1021/accountsmr.4c0040410.1021/accountsmr.4c00404","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00404https://doi.org/10.1021/accountsmr.4c00404","url":null,"abstract":"<p >Carbon is an abundant material with remarkable thermal, mechanical, physical, and chemical properties. Each allotrope has unique structures, properties, functionalities, and corresponding applications. Over the past few decades, various types of carbon materials such as graphene, carbon nanotubes, carbon quantum dots, and carbon fibers have been produced, finding applications in energy conversion and storage, water treatment, sensing, polymer composites, and biomedical fields. Among these carbon materials, porous carbons are highly interesting owing to their large surface areas and massive active sites to interact with molecules, ions, and other chemical species. The pore size and pore size distributions can be tunable (micro-, meso-, and macro-pores), providing chemical species with hierarchical structures to transport with low resistances. In this context, designing carbon precursors and preparing porous carbon with desired structures, properties, and functionalities are highly significant.</p><p >Polymers are versatile carbon precursors. Designing the polymer precursors that facilitate the formation of well-controlled pores is an effective strategy to prepare porous carbons. In particular, porous carbon fibers (PCFs) in a fibrous format offer additional features of hierarchical porosity control, increased surface area, and fast ion transport. The most common approach to synthesizing PCFs is to use sacrificial agents (e.g., homopolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA), inorganic nanoparticles, and other additives) in a matrix of polyacrylonitrile (PAN) as the carbon fiber precursor. However, the nonuniform mixing of sacrificial agents in the PAN matrix results in PCFs with nonuniform pores and wide pore size distributions. Moreover, complete removal of the inorganic additives is challenging and sometimes requires the use of hazardous chemicals. Therefore, developing innovative methods for synthesizing PCFs is imperative to advance these engineering materials for emerging applications.</p><p >In this Account, we summarize our efforts on the use of block copolymer precursors to prepare PCFs with tunable pore sizes and pore size distributions for a series of applications. First, we will introduce the synthesis methodologies for preparing PCFs. We have used reversible addition–fragmentation chain transfer (RAFT) polymerization to synthesize block copolymer precursors. Second, we will discuss the effects of preparation conditions on the properties of PCFs. The mechanical and electrical properties highly depend on the composition of the block copolymer, pyrolysis conditions, and humidity level during the fiber spinning process. Lastly, we will discuss the effects of controlled porosity on the surface area, electrical/ionic conductivity, and polymer-matrix interactions, which are crucial for applications including energy storage (e.g., batteries and supercapacitors), fiber-reinforced polymer composites, separation, and fil","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 3","pages":"366–378 366–378"},"PeriodicalIF":14.0,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/accountsmr.4c00404","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713893","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Block Copolymer Based Porous Carbon Fiber─Synthesis, Processing, and Applications","authors":"Adeel Zia, Yue Zhang, Akshara Paras Parekh, Guoliang Liu","doi":"10.1021/accountsmr.4c00404","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00404","url":null,"abstract":"Carbon is an abundant material with remarkable thermal, mechanical, physical, and chemical properties. Each allotrope has unique structures, properties, functionalities, and corresponding applications. Over the past few decades, various types of carbon materials such as graphene, carbon nanotubes, carbon quantum dots, and carbon fibers have been produced, finding applications in energy conversion and storage, water treatment, sensing, polymer composites, and biomedical fields. Among these carbon materials, porous carbons are highly interesting owing to their large surface areas and massive active sites to interact with molecules, ions, and other chemical species. The pore size and pore size distributions can be tunable (micro-, meso-, and macro-pores), providing chemical species with hierarchical structures to transport with low resistances. In this context, designing carbon precursors and preparing porous carbon with desired structures, properties, and functionalities are highly significant.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"20 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077144","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":"Constructing High-Performance Heterogeneous Catalysts through Interface Engineering on Metal–Organic Framework Platforms","authors":"Bo Li, Jian-Gong Ma, Peng Cheng","doi":"10.1021/accountsmr.4c00367","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00367","url":null,"abstract":"Heterogeneous catalysis has pushed the modern chemical industry to an unprecedented level of development, especially in the past century, where catalytic processes have made significant contributions to the prosperity of the global economy and the modernization of human lifestyles. 80% of chemical processes involve catalytic technology. From the production of fertilizers and the synthesis of high-performance polymers to the development of anticancer drugs, catalysts mediate the occurrence of these chemical processes. Developing efficient, stable, and low-energy heterogeneous catalysts is the key to a sustainable future. Most industrial heterogeneous catalysts typically load highly dispersed active components at the nanoscale onto porous solid supports, which have a large specific surface area. Among the numerous candidates for porous materials, the construction of high-performance heterogeneous catalyst systems through interface engineering on metal–organic framework (MOF) platforms has recently received great attention. Compared with traditional porous materials, MOFs provide a huge active interface for catalytic reactions due to their large specific surface area and porosity. Their extraordinary skeleton structure provides many possibilities for integrating various functional building blocks. At the same time, as crystalline materials with diverse structures, their well-defined atomically precise structure provides an ideal platform for customized design and synthesis of catalysts as well as in-depth exploration of the structure–activity relationship between the structure of catalyst and the catalytic performance. After more than a decade of development, interface engineering has played a significant role in the development of MOF-based heterogeneous catalysts. Therefore, it is timely to summarize the latest developments in this field, which will provide guidance for future research and achieve green, low-carbon, and sustainable modern industries.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"77 4 Pt 1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077143","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":"Why and How to Investigate Biological Materials Processing: A Cross-Disciplinary Approach for Inspiring Sustainable Materials Fabrication","authors":"Matthew J. Harrington","doi":"10.1021/accountsmr.4c00334","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00334","url":null,"abstract":"Enhancing the performance and sustainability of materials is a major challenge facing humanity. With nearly 400 million tons of plastics manufactured per year and plastic waste accumulation of 12 billion tons expected by 2050, the production and buildup of anthropogenic petroleum-based waste is a major threat to our global ecosystem. This impending environmental catastrophe demands alternative sustainable and circular routes for material production. Additionally, there is a need for new polymeric materials that possess properties not currently found in synthetic materials for various applications in biomedical engineering, soft robotics, flexible electronics, and more. Nature offers inspiration for solving both of these environmentally, economically, and socially impactful global issues. Indeed, living organisms, such as spiders and mussels, rapidly fabricate polymeric biological materials from biomolecular building blocks (e.g., proteins) under green, environmentally benign processing conditions. These materials exhibit properties that surpass many synthetic plastics (e.g., high toughness, self-healing, “smart” adaptability, underwater adhesion), providing a blueprint for how humans can develop sustainable fabrication practices for producing next-generation materials. There is now a solid understanding of the structure–function relationships defining the performance of many biological materials, with control of structural hierarchy from nanoscale to centimeter scale emerging as a common design feature. Yet, it has been extremely challenging to replicate this hierarchical structure and, thus, the relevant properties in synthetic materials. This is largely due to a poor understanding of how these materials are fabricated by living organisms. Indeed, elucidation of the physicochemical principles underlying the fabrication of these and similar materials is significantly hampered due to experimental challenges in following these dynamic processes at the relevant spatiotemporal scales. Here, I outline a cross-disciplinary experimental approach spanning organismal biology, molecular biology, biochemistry, physical chemistry, and materials science for extracting design principles from biofabrication processes. As a model system, I focus on the fabrication of the mussel byssus–a biopolymeric fibrous holdfast with outstanding properties (underwater adhesion, high toughness, self-healing capacity) that is an established archetype for sustainable bioinspired fibers, glues, composites, and coatings. Careful analysis combining traditional histology and biochemical approaches with advanced spectroscopic imaging (e.g, confocal Raman spectroscopy, FTIR spectroscopy, and micro X-ray fluorescence), tomographic approaches (e.g., micro-CT), and advanced electron microscopy (e.g., focused ion beam scanning electron microscopy (FIB-SEM)) have yielded deep insights into the byssus assembly process, highlighting the key role of fluid protein condensates (liquid crystals","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"59 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050133","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":"Why and How to Investigate Biological Materials Processing: A Cross-Disciplinary Approach for Inspiring Sustainable Materials Fabrication","authors":"Matthew J. Harrington*, ","doi":"10.1021/accountsmr.4c0033410.1021/accountsmr.4c00334","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00334https://doi.org/10.1021/accountsmr.4c00334","url":null,"abstract":"<p >Enhancing the performance and sustainability of materials is a major challenge facing humanity. With nearly 400 million tons of plastics manufactured per year and plastic waste accumulation of 12 billion tons expected by 2050, the production and buildup of anthropogenic petroleum-based waste is a major threat to our global ecosystem. This impending environmental catastrophe demands alternative sustainable and circular routes for material production. Additionally, there is a need for new polymeric materials that possess properties not currently found in synthetic materials for various applications in biomedical engineering, soft robotics, flexible electronics, and more. Nature offers inspiration for solving both of these environmentally, economically, and socially impactful global issues. Indeed, living organisms, such as spiders and mussels, rapidly fabricate polymeric biological materials from biomolecular building blocks (e.g., proteins) under green, environmentally benign processing conditions. These materials exhibit properties that surpass many synthetic plastics (e.g., high toughness, self-healing, “smart” adaptability, underwater adhesion), providing a blueprint for how humans can develop sustainable fabrication practices for producing next-generation materials. There is now a solid understanding of the structure–function relationships defining the performance of many biological materials, with control of structural hierarchy from nanoscale to centimeter scale emerging as a common design feature. Yet, it has been extremely challenging to replicate this hierarchical structure and, thus, the relevant properties in synthetic materials. This is largely due to a poor understanding of how these materials are fabricated by living organisms. Indeed, elucidation of the physicochemical principles underlying the fabrication of these and similar materials is significantly hampered due to experimental challenges in following these dynamic processes at the relevant spatiotemporal scales. Here, I outline a cross-disciplinary experimental approach spanning organismal biology, molecular biology, biochemistry, physical chemistry, and materials science for extracting design principles from biofabrication processes. As a model system, I focus on the fabrication of the mussel byssus–a biopolymeric fibrous holdfast with outstanding properties (underwater adhesion, high toughness, self-healing capacity) that is an established archetype for sustainable bioinspired fibers, glues, composites, and coatings. Careful analysis combining traditional histology and biochemical approaches with advanced spectroscopic imaging (e.g, confocal Raman spectroscopy, FTIR spectroscopy, and micro X-ray fluorescence), tomographic approaches (e.g., micro-CT), and advanced electron microscopy (e.g., focused ion beam scanning electron microscopy (FIB-SEM)) have yielded deep insights into the byssus assembly process, highlighting the key role of fluid protein condensates (liquid crys","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 3","pages":"294–305 294–305"},"PeriodicalIF":14.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143714036","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":"Molecule-Based Crystalline Adsorbents: Advancing Adsorption Theory and Storage/Separation Applications","authors":"Xue-Wen Zhang, Jie-Peng Zhang, Xiao-Ming Chen","doi":"10.1021/accountsmr.4c00316","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00316","url":null,"abstract":"As a simple and common physicochemical process, adsorption is the basis of storage, separation, and many other applications. Compared to conventional adsorbents, molecule-based crystalline materials show advantages of extremely rich and easily designable/synthesized/characterized structures as well as remarkable flexibility. The emergence of new adsorbent materials has brought forth both opportunities and challenges for adsorption theory and its applications.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"75 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020942","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":"Molecule-Based Crystalline Adsorbents: Advancing Adsorption Theory and Storage/Separation Applications","authors":"Xue-Wen Zhang, Jie-Peng Zhang* and Xiao-Ming Chen, ","doi":"10.1021/accountsmr.4c0031610.1021/accountsmr.4c00316","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00316https://doi.org/10.1021/accountsmr.4c00316","url":null,"abstract":"<p >As a simple and common physicochemical process, adsorption is the basis of storage, separation, and many other applications. Compared to conventional adsorbents, molecule-based crystalline materials show advantages of extremely rich and easily designable/synthesized/characterized structures as well as remarkable flexibility. The emergence of new adsorbent materials has brought forth both opportunities and challenges for adsorption theory and its applications.</p><p >Focusing on the simplest applications of adsorption, i.e., storage and separation, this Account aims to analyze the representative adsorbent engineering strategies. First, we provide a brief introduction to conventional adsorption theory and the fundamental principles of adsorptive storage and separation applications. Following that, we discuss how the special structural characteristics of molecule-based crystalline adsorbents, especially their flexibility, provide new insights and directions.</p><p >According to the well-established adsorption theory, molecule-based crystalline porous materials offer not only exceptionally large pore volumes and specific surface areas but also a wide variety of adsorption sites with a tunable guest binding affinity. More importantly, the concentration and position of the adsorption sites can be engineered and straightforwardly visualized. By rationally tuning host–guest and guest–guest interactions, the adsorption isotherm shape can be regulated to increase working capacity and selectivity and even inverse selectivity to meet practical separation demands.</p><p >Inspired by the structural flexibility of molecule-based crystalline materials, we need to consider the structural transformations of host–guest systems in the adsorption processes, in not only the thermodynamic but also the kinetic aspects. Rational classification of the various types of flexibility or structural transformations is crucial for elucidating the structure–property relationships in these host–guest systems. As the most well-known type of flexibility, guest-induced crystal-to-crystal structural transformations are thermodynamically controlled and occur periodically at the equilibrium state, which can be conveniently and straightforwardly visualized by diffraction techniques. Particularly, the pore-opening action (nonporous-to-porous transformation) can offer exceptionally high working capacity and remarkable advantages in terms of thermal effects. In the matter of crystalline adsorbents, this flexibility can also be aperiodic, which can effectively address the coadsorption and leakage issues to give high adsorption selectivity and purification productivity. The structural flexibility of host–guest systems can also be kinetically controlled and occur at the nonequilibrium state (and aperiodically). Gating flexibility describes the transient structural transformations for diffusion of oversized guest molecules, which not only provides more comprehensive mechanisms and criteria","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"6 3","pages":"259–273 259–273"},"PeriodicalIF":14.0,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143714034","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}