Pub Date : 2025-02-21DOI: 10.1021/accountsmr.4c00359
Jignesh S. Mahajan, Eric R. Gottlieb, Jung Min Kim, Thomas H. Epps, III
Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable, high-performance, polymeric materials. Although lignin is a highly available and low-cost source of natural aromatics, it is commonly burned for heat or disposed of as waste. The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds. These considerations are derived from two fundamental aspects of lignin: its recalcitrant/heterogeneous nature and aromatic methoxy substituents. This Account highlights four key efforts from the Epps group and collaborators that established innovative methods/processes to synthesize polymers from lignin deconstruction products to unlock application potential, with a particular focus on the polymerization of biobased monomer mixtures, development of structure–property–processing relationships for diverse feedstocks, functional benefits of methoxy substituents, and scalability of lignin deconstruction.
{"title":"Toward Sustainable Materials: From Lignocellulosic Biomass to High-Performance Polymers","authors":"Jignesh S. Mahajan, Eric R. Gottlieb, Jung Min Kim, Thomas H. Epps, III","doi":"10.1021/accountsmr.4c00359","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00359","url":null,"abstract":"Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable, high-performance, polymeric materials. Although lignin is a highly available and low-cost source of natural aromatics, it is commonly burned for heat or disposed of as waste. The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds. These considerations are derived from two fundamental aspects of lignin: its recalcitrant/heterogeneous nature and aromatic methoxy substituents. This Account highlights four key efforts from the Epps group and collaborators that established innovative methods/processes to synthesize polymers from lignin deconstruction products to unlock application potential, with a particular focus on the polymerization of biobased monomer mixtures, development of structure–property–processing relationships for diverse feedstocks, functional benefits of methoxy substituents, and scalability of lignin deconstruction.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"80 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463265","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}
Pub Date : 2025-02-19DOI: 10.1021/accountsmr.4c00337
Wei Gong, Yifei Gao, Jinqiao Dong, Yan Liu, Yong Cui
Reticular chemistry, pioneered by Omar Yaghi, is concerned with linking molecular building blocks into porous crystalline 2D or 3D architectures through coordination bonds (metal–organic frameworks, MOFs) or covalent bonds (covalent organic frameworks, COFs). The successful marriage of inorganic and organic chemistry in MOFs has provided vast combinations amenable to manufacturing enormous solid materials (>100,000 in Cambridge Crystallographic Data Centre) with atomic precision. Benefiting from the immanent component and structural diversity, as well as the accessible nanometer-scale spaces within which various matter can be manipulated and controlled, the reticular framework materials have in effect not only facilitated the development of basic chemistry but also revolutionized various fields of applications including gas storage and separation, heterogeneous catalysis, heat allocation, sensors, photovoltaics, fuel cells, and biomedicine, to just name a few. One particularly intriguing subset of reticular frameworks concerns those that have chiral elements or characteristics, which represent a unique class of extended porous solids that can implement enantiomerically selective applications and beyond. However, the development of this field is still at the embryonic stage as compared with that of achiral reticular frameworks. Herein, we summarize the progress in the development of “chiral reticular chemistry” through which a serial of homochiral or racemic reticular frameworks with novel topologies and functions can be targeted. To begin, we introduce the background of reticular chemistry and the potential of using chiral building blocks to assemble reticular frameworks, particularly MOFs. In the following section, we describe the synthetic diversity and complexity using enantiopure or racemic ligands and highlight the important role of enantiopurity engineering in affecting the ultimate products. To be more specific, we present (i) isotopological synthesis in which enantiopure or racemic ligands produce frameworks with the same net topology, where the racemic ligands form either racemic frameworks or conglomerates; (ii) intrinsically chiral net-dominated synthesis in which enantiopure or racemic ligands can form different underlying topologies or undergo distinct crystallization pathways; (iii) other atypical syntheses that typically come by way of serendipity, where the assembly mechanism is highly elusive (for example, the enantiomeric ligands of opposite chirality give rise to entirely different structures). Next, we discuss the applications of these unique reticular framework materials that are otherwise unachievable by conventional achiral materials or analogues, aiming to underline the unique role of chiral building blocks in reticular chemistry. Last, we point out future research directions of “chiral reticular chemistry”. Our Account aims to highlight the importance of chirality as a decisive parameter to control the ultimate structu
{"title":"Chiral Reticular Chemistry toward Functional Materials Discovery and Beyond","authors":"Wei Gong, Yifei Gao, Jinqiao Dong, Yan Liu, Yong Cui","doi":"10.1021/accountsmr.4c00337","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00337","url":null,"abstract":"Reticular chemistry, pioneered by Omar Yaghi, is concerned with linking molecular building blocks into porous crystalline 2D or 3D architectures through coordination bonds (metal–organic frameworks, MOFs) or covalent bonds (covalent organic frameworks, COFs). The successful marriage of inorganic and organic chemistry in MOFs has provided vast combinations amenable to manufacturing enormous solid materials (>100,000 in Cambridge Crystallographic Data Centre) with atomic precision. Benefiting from the immanent component and structural diversity, as well as the accessible nanometer-scale spaces within which various matter can be manipulated and controlled, the reticular framework materials have in effect not only facilitated the development of basic chemistry but also revolutionized various fields of applications including gas storage and separation, heterogeneous catalysis, heat allocation, sensors, photovoltaics, fuel cells, and biomedicine, to just name a few. One particularly intriguing subset of reticular frameworks concerns those that have chiral elements or characteristics, which represent a unique class of extended porous solids that can implement enantiomerically selective applications and beyond. However, the development of this field is still at the embryonic stage as compared with that of achiral reticular frameworks. Herein, we summarize the progress in the development of “chiral reticular chemistry” through which a serial of homochiral or racemic reticular frameworks with novel topologies and functions can be targeted. To begin, we introduce the background of reticular chemistry and the potential of using chiral building blocks to assemble reticular frameworks, particularly MOFs. In the following section, we describe the synthetic diversity and complexity using enantiopure or racemic ligands and highlight the important role of enantiopurity engineering in affecting the ultimate products. To be more specific, we present (i) isotopological synthesis in which enantiopure or racemic ligands produce frameworks with the same net topology, where the racemic ligands form either racemic frameworks or conglomerates; (ii) intrinsically chiral net-dominated synthesis in which enantiopure or racemic ligands can form different underlying topologies or undergo distinct crystallization pathways; (iii) other atypical syntheses that typically come by way of serendipity, where the assembly mechanism is highly elusive (for example, the enantiomeric ligands of opposite chirality give rise to entirely different structures). Next, we discuss the applications of these unique reticular framework materials that are otherwise unachievable by conventional achiral materials or analogues, aiming to underline the unique role of chiral building blocks in reticular chemistry. Last, we point out future research directions of “chiral reticular chemistry”. Our Account aims to highlight the importance of chirality as a decisive parameter to control the ultimate structu","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"15 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451825","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}
Pub Date : 2025-02-19DOI: 10.1021/accountsmr.4c00338
Xinyu Zhang, Youzhi Xu, Pingwu Du
Topologically unique nanocarbon materials with optoelectronic potential are both fascinating and challenging synthetic targets. Their distinctive molecular topologies often lead to chirality, unique optoelectronic properties, and encapsulation capabilities, stimulating advances in synthetic chemistry and materials science. The research on curved nanocarbon materials has garnered substantial interest due to the intricate relationship between their π-conjugation and molecular geometry, as well as their emerging applications in various fields. The introduction of curvature significantly affects the redox behaviors, optical properties, charge-transport capabilities, and self-assembly processes of these nanocarbon materials. The representative examples of curved aromatic systems are cycloparaphenylenes (CPPs) and related carbon nanorings. In these molecules, the nonplanar aromatic structures can induce unique radial π-conjugation and further endow them with distinctive photophysical properties. By adjusting the number of benzene rings in a CPP or incorporating diverse polycyclic aromatic hydrocarbon units, researchers can finely tune the optical and electronic properties of these nanostructures. Many potential applications can be discovered in the fields of fluorescent probes, organic light-emitting diodes (OLEDs), and optoelectronic devices. These properties establish CPP as an important scaffold to create novel carbon nanostructures. With the ongoing advancements in molecular topology, new opportunities are emerging within the fields of materials science, molecular electronics, and biomedicine. Given the exceptional electronic and photophysical properties of CPPs, there has been considerable interest in the development of topologically intriguing bis/multimacrocyclic architectures. It is anticipated that high dimensionality and unexplored topologies will endow these bis/multimacrocycles with unparalleled physical and chemical properties. This concise Account highlights recent developments from our research group on topologically functional materials based on CPP carbon nanorings, particularly their potential applications. Our discussion focuses on (i) the design and synthesis of a series of fully <i>sp</i><sup>2</sup>-hybridized all-benzenoid bismacrocycles, as well as [n]cycloparaphenylene-pillar[5]arene bismacrocycles; (ii) the construction of all-CPP-based long π-extended polymeric segments of the armchair SWCNT; and (iii) the synthesis of CPP-based mechanically interlocked molecules, specifically [12]CPP-[3]catenane. Structures like these CPP-based bis/multimacrocyclic architectures exhibit distinct properties─including radial π-conjugation, supramolecular properties, chirality, and unexpected dual-emissive and anti-Kasha photophysical characteristics due to their nonplanar geometries─that allow precise tuning of their HOMO–LUMO gap, emission profiles, and charge-transport behaviors. These properties make them promising for applications in OLEDs
{"title":"Functional Bis/Multimacrocyclic Materials Based on Cycloparaphenylene Carbon Nanorings","authors":"Xinyu Zhang, Youzhi Xu, Pingwu Du","doi":"10.1021/accountsmr.4c00338","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00338","url":null,"abstract":"Topologically unique nanocarbon materials with optoelectronic potential are both fascinating and challenging synthetic targets. Their distinctive molecular topologies often lead to chirality, unique optoelectronic properties, and encapsulation capabilities, stimulating advances in synthetic chemistry and materials science. The research on curved nanocarbon materials has garnered substantial interest due to the intricate relationship between their π-conjugation and molecular geometry, as well as their emerging applications in various fields. The introduction of curvature significantly affects the redox behaviors, optical properties, charge-transport capabilities, and self-assembly processes of these nanocarbon materials. The representative examples of curved aromatic systems are cycloparaphenylenes (CPPs) and related carbon nanorings. In these molecules, the nonplanar aromatic structures can induce unique radial π-conjugation and further endow them with distinctive photophysical properties. By adjusting the number of benzene rings in a CPP or incorporating diverse polycyclic aromatic hydrocarbon units, researchers can finely tune the optical and electronic properties of these nanostructures. Many potential applications can be discovered in the fields of fluorescent probes, organic light-emitting diodes (OLEDs), and optoelectronic devices. These properties establish CPP as an important scaffold to create novel carbon nanostructures. With the ongoing advancements in molecular topology, new opportunities are emerging within the fields of materials science, molecular electronics, and biomedicine. Given the exceptional electronic and photophysical properties of CPPs, there has been considerable interest in the development of topologically intriguing bis/multimacrocyclic architectures. It is anticipated that high dimensionality and unexplored topologies will endow these bis/multimacrocycles with unparalleled physical and chemical properties. This concise Account highlights recent developments from our research group on topologically functional materials based on CPP carbon nanorings, particularly their potential applications. Our discussion focuses on (i) the design and synthesis of a series of fully <i>sp</i><sup>2</sup>-hybridized all-benzenoid bismacrocycles, as well as [n]cycloparaphenylene-pillar[5]arene bismacrocycles; (ii) the construction of all-CPP-based long π-extended polymeric segments of the armchair SWCNT; and (iii) the synthesis of CPP-based mechanically interlocked molecules, specifically [12]CPP-[3]catenane. Structures like these CPP-based bis/multimacrocyclic architectures exhibit distinct properties─including radial π-conjugation, supramolecular properties, chirality, and unexpected dual-emissive and anti-Kasha photophysical characteristics due to their nonplanar geometries─that allow precise tuning of their HOMO–LUMO gap, emission profiles, and charge-transport behaviors. These properties make them promising for applications in OLEDs","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"38 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463269","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}
Pub Date : 2025-02-12DOI: 10.1021/accountsmr.4c00318
Lixin Jiang, Lang Qin, Feng Pan, Yanlei Yu
The microfluidic biochemical/immunoassay systems typically consist of microfluidic chips, fluid driving devices, and detection components. The core of the system is the microfluidic chips based on microfluidic technology, which are typically constructed with nonresponsive materials such as silicon, glass, and rigid plastics, thus requiring complex external air/liquid pumps to manipulate the samples. The external equipment renders the microfluidic systems cumbersome and increases the risk of biosample contamination. The all-optical microfluidic chip (AOMC) integrates all necessary microfluidic units and uses light to manipulate microfluids, which has the potential to completely solve the major problems of miniaturization and integration in microfluidic systems. The photocontrolled manipulation in AOMCs facilitates contactless interaction with liquids, eliminating the need for physical interconnects such as complex external electric, hydraulic, or pneumatic devices and replacing the traditional microfluidic components such as pumps, mixers, and separators, which offers AOMCs improved flexibility, robustness, and portability. However, impeded by photocontrolled principles and appropriate materials, AOMCs and photocontrolled biochemical/immunoassay analyzers have never been created.
{"title":"All-Optical Microfluidic Technology Enabled by Photodeformable Linear Liquid Crystal Polymers","authors":"Lixin Jiang, Lang Qin, Feng Pan, Yanlei Yu","doi":"10.1021/accountsmr.4c00318","DOIUrl":"https://doi.org/10.1021/accountsmr.4c00318","url":null,"abstract":"The microfluidic biochemical/immunoassay systems typically consist of microfluidic chips, fluid driving devices, and detection components. The core of the system is the microfluidic chips based on microfluidic technology, which are typically constructed with nonresponsive materials such as silicon, glass, and rigid plastics, thus requiring complex external air/liquid pumps to manipulate the samples. The external equipment renders the microfluidic systems cumbersome and increases the risk of biosample contamination. The all-optical microfluidic chip (AOMC) integrates all necessary microfluidic units and uses light to manipulate microfluids, which has the potential to completely solve the major problems of miniaturization and integration in microfluidic systems. The photocontrolled manipulation in AOMCs facilitates contactless interaction with liquids, eliminating the need for physical interconnects such as complex external electric, hydraulic, or pneumatic devices and replacing the traditional microfluidic components such as pumps, mixers, and separators, which offers AOMCs improved flexibility, robustness, and portability. However, impeded by photocontrolled principles and appropriate materials, AOMCs and photocontrolled biochemical/immunoassay analyzers have never been created.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"40 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393781","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}
Pub Date : 2025-02-03DOI: 10.1021/accountsmr.5c00007
Keunhyuk Ryu, Gang Li, Keyi Zhang, Jianguo Guan, Yi Long, ZhiLi Dong
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.
{"title":"Thermoresponsive Hydrogels for the Construction of Smart Windows, Sensors, and Actuators","authors":"Keunhyuk Ryu, Gang Li, Keyi Zhang, Jianguo Guan, Yi Long, ZhiLi Dong","doi":"10.1021/accountsmr.5c00007","DOIUrl":"https://doi.org/10.1021/accountsmr.5c00007","url":null,"abstract":"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.","PeriodicalId":72040,"journal":{"name":"Accounts of materials research","volume":"12 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077142","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}
Pub Date : 2025-02-03DOI: 10.1021/accountsmr.4c00343
Pengyu Zhang, Ting Zhang
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.
{"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}
Pub Date : 2025-02-02DOI: 10.1021/accountsmr.4c00404
Adeel Zia, Yue Zhang, Akshara Paras Parekh, Guoliang Liu
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.
{"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}
Pub Date : 2025-02-02DOI: 10.1021/accountsmr.4c00367
Bo Li, Jian-Gong Ma, Peng Cheng
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.
{"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}
Pub Date : 2025-01-27DOI: 10.1021/accountsmr.4c00334
Matthew J. Harrington
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
{"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}
Pub Date : 2025-01-23DOI: 10.1021/accountsmr.4c00316
Xue-Wen Zhang, Jie-Peng Zhang, Xiao-Ming Chen
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.
{"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}
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