Global population growth and industrialization have exacerbated the nonrenewable energy crises and environmental issues, thereby stimulating an enormous demand for producing environmentally friendly materials. Typically, biomass-based aerogels (BAs), which are mainly composed of biomass materials, show great application prospects in various fields because of their exceptional properties such as biocompatibility, degradability, and renewability. To improve the performance of BAs to meet the usage requirements of different scenarios, a large number of innovative works in the past few decades have emphasized the importance of micro-structural design in regulating macroscopic functions. Inspired by the ubiquitous random or regularly arranged structures of materials in nature ranging from micro to meso and macro scales, constructing different microstructures often corresponds to completely different functions even with similar biomolecular compositions. This review focuses on the preparation process, design concepts, regulation methods, and the synergistic combination of chemical compositions and microstructures of BAs with different porous structures from the perspective of gel skeleton and pore structure. It not only comprehensively introduces the effect of various microstructures on the physical properties of BAs, but also analyzes their potential applications in the corresponding fields of thermal management, water treatment, atmospheric water harvesting, CO2 absorption, energy storage and conversion, electromagnetic interference (EMI) shielding, biological applications, etc. Finally, we provide our perspectives regarding the challenges and future opportunities of BAs. Overall, our goal is to provide researchers with a thorough understanding of the relationship between the microstructures and properties of BAs, supported by a comprehensive analysis of the available data.
全球人口增长和工业化加剧了不可再生能源危机和环境问题,从而激发了对生产环保材料的巨大需求。通常,以生物质材料为主要成分的生物质气凝胶(BAs)因其生物相容性、可降解性和可再生性等优异特性,在各个领域都显示出巨大的应用前景。为了提高生物质吸附剂的性能以满足不同应用场景的使用要求,过去几十年来,大量创新工作都强调了微观结构设计在调节宏观功能方面的重要性。受自然界从微观到中观和宏观尺度无处不在的随机或规则排列材料结构的启发,即使生物分子组成相似,构建不同的微观结构往往对应着完全不同的功能。本综述从凝胶骨架和孔隙结构的角度,重点介绍了具有不同多孔结构的生物碱的制备过程、设计理念、调控方法以及化学成分与微结构的协同组合。不仅全面介绍了各种微结构对 BA 物理性质的影响,还分析了 BA 在热管理、水处理、大气水收集、二氧化碳吸收、能量存储和转换、电磁干扰(EMI)屏蔽、生物应用等相应领域的潜在应用。最后,我们就生物曝气阱面临的挑战和未来的机遇提出了自己的看法。总之,我们的目标是通过对现有数据的全面分析,让研究人员透彻地了解 BA 的微观结构与性能之间的关系。
{"title":"Renewable biomass-based aerogels: from structural design to functional regulation.","authors":"Linfeng Chen, Xiaoxiao Yu, Mengyue Gao, Chengjian Xu, Junyan Zhang, Xinhai Zhang, Meifang Zhu, Yanhua Cheng","doi":"10.1039/d3cs01014g","DOIUrl":"https://doi.org/10.1039/d3cs01014g","url":null,"abstract":"<p><p>Global population growth and industrialization have exacerbated the nonrenewable energy crises and environmental issues, thereby stimulating an enormous demand for producing environmentally friendly materials. Typically, biomass-based aerogels (BAs), which are mainly composed of biomass materials, show great application prospects in various fields because of their exceptional properties such as biocompatibility, degradability, and renewability. To improve the performance of BAs to meet the usage requirements of different scenarios, a large number of innovative works in the past few decades have emphasized the importance of micro-structural design in regulating macroscopic functions. Inspired by the ubiquitous random or regularly arranged structures of materials in nature ranging from micro to meso and macro scales, constructing different microstructures often corresponds to completely different functions even with similar biomolecular compositions. This review focuses on the preparation process, design concepts, regulation methods, and the synergistic combination of chemical compositions and microstructures of BAs with different porous structures from the perspective of gel skeleton and pore structure. It not only comprehensively introduces the effect of various microstructures on the physical properties of BAs, but also analyzes their potential applications in the corresponding fields of thermal management, water treatment, atmospheric water harvesting, CO<sub>2</sub> absorption, energy storage and conversion, electromagnetic interference (EMI) shielding, biological applications, <i>etc.</i> Finally, we provide our perspectives regarding the challenges and future opportunities of BAs. Overall, our goal is to provide researchers with a thorough understanding of the relationship between the microstructures and properties of BAs, supported by a comprehensive analysis of the available data.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141416704","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Atmospheric water harvesting (AWH) is recognized as a crucial strategy to address the global challenge of water scarcity by tapping into the vast reserves of atmospheric moisture for potable water supply. Within this domain, sorbents lie in the core of AWH technologies as they possess broad adaptability across a wide spectrum of humidity levels, underpinned by the cyclic sorption and desorption processes of sorbents, necessitating a multi-scale viewpoint regarding the rational material and chemical selection and design. This Invited Review delves into the essential sorption mechanisms observed across various classes of sorbent systems, emphasizing the water-sorbent interactions and the progression of water networks. A special focus is placed on the insights derived from isotherm profiles, which elucidate sorbent structures and sorption dynamics. From these foundational principles, we derive material and chemical design guidelines and identify key tuning factors from a structural-functional perspective across multiple material systems, addressing their fundamental chemistries and unique attributes. The review further navigates through system-level design considerations to optimize water production efficiency. This review aims to equip researchers in the field of AWH with a thorough understanding of the water-sorbent interactions, material design principles, and system-level considerations essential for advancing this technology.
{"title":"Chemistries and materials for atmospheric water harvesting.","authors":"Chuxin Lei, Weixin Guan, Yaxuan Zhao, Guihua Yu","doi":"10.1039/d4cs00423j","DOIUrl":"https://doi.org/10.1039/d4cs00423j","url":null,"abstract":"<p><p>Atmospheric water harvesting (AWH) is recognized as a crucial strategy to address the global challenge of water scarcity by tapping into the vast reserves of atmospheric moisture for potable water supply. Within this domain, sorbents lie in the core of AWH technologies as they possess broad adaptability across a wide spectrum of humidity levels, underpinned by the cyclic sorption and desorption processes of sorbents, necessitating a multi-scale viewpoint regarding the rational material and chemical selection and design. This Invited Review delves into the essential sorption mechanisms observed across various classes of sorbent systems, emphasizing the water-sorbent interactions and the progression of water networks. A special focus is placed on the insights derived from isotherm profiles, which elucidate sorbent structures and sorption dynamics. From these foundational principles, we derive material and chemical design guidelines and identify key tuning factors from a structural-functional perspective across multiple material systems, addressing their fundamental chemistries and unique attributes. The review further navigates through system-level design considerations to optimize water production efficiency. This review aims to equip researchers in the field of AWH with a thorough understanding of the water-sorbent interactions, material design principles, and system-level considerations essential for advancing this technology.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141416703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Covalent organic frameworks (COFs) have recently seen significant advancements. Large quantities of structurally & functionally oriented COFs with a wide range of applications, such as gas adsorption, catalysis, separation, and drug delivery, have been explored. Recent achievements in this field are primarily focused on advancing synthetic methodologies, with catalysts playing a crucial role in achieving highly crystalline COF materials, particularly those featuring novel linkages and chemistry. A series of reviews have already been published over the last decade, covering the fundamentals, synthesis, and applications of COFs. However, despite the pivotal role that catalysts and auxiliaries play in forming COF materials and adjusting their properties (e.g., crystallinity, porosity, stability, and morphology), limited attention has been devoted to these essential components. In this Critical Review, we mainly focus on the state-of-the-art progress of catalysts and auxiliaries applied to the synthesis of COFs. The catalysts include four categories: acid catalysts, base catalysts, transition-metal catalysts, and other catalysts. The auxiliaries, such as modulators, oxygen, and surfactants, are discussed as well. This is then followed by the description of several specific applications derived from the utilization of catalysts and auxiliaries. Lastly, a perspective on the major challenges and opportunities associated with catalysts and auxiliaries is provided.
{"title":"The development of catalysts and auxiliaries for the synthesis of covalent organic frameworks.","authors":"Wei Zhao, Qiang Zhu, Xiaofeng Wu, Dan Zhao","doi":"10.1039/d3cs00908d","DOIUrl":"https://doi.org/10.1039/d3cs00908d","url":null,"abstract":"<p><p>Covalent organic frameworks (COFs) have recently seen significant advancements. Large quantities of structurally & functionally oriented COFs with a wide range of applications, such as gas adsorption, catalysis, separation, and drug delivery, have been explored. Recent achievements in this field are primarily focused on advancing synthetic methodologies, with catalysts playing a crucial role in achieving highly crystalline COF materials, particularly those featuring novel linkages and chemistry. A series of reviews have already been published over the last decade, covering the fundamentals, synthesis, and applications of COFs. However, despite the pivotal role that catalysts and auxiliaries play in forming COF materials and adjusting their properties (<i>e.g.</i>, crystallinity, porosity, stability, and morphology), limited attention has been devoted to these essential components. In this Critical Review, we mainly focus on the state-of-the-art progress of catalysts and auxiliaries applied to the synthesis of COFs. The catalysts include four categories: acid catalysts, base catalysts, transition-metal catalysts, and other catalysts. The auxiliaries, such as modulators, oxygen, and surfactants, are discussed as well. This is then followed by the description of several specific applications derived from the utilization of catalysts and auxiliaries. Lastly, a perspective on the major challenges and opportunities associated with catalysts and auxiliaries is provided.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141416639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaowen Sun, Rafael B Araujo, Egon Campos Dos Santos, Yuanhua Sang, Hong Liu, Xiaowen Yu
Descriptors play a crucial role in electrocatalysis as they can provide valuable insights into the electrochemical performance of energy conversion and storage processes. They allow for the understanding of different catalytic activities and enable the prediction of better catalysts without relying on the time-consuming trial-and-error approaches. Hence, this comprehensive review focuses on highlighting the significant advancements in commonly used descriptors for critical electrocatalytic reactions. First, the fundamental reaction processes and key intermediates involved in several electrocatalytic reactions are summarized. Subsequently, three types of descriptors are classified and introduced based on different reactions and catalysts. These include d-band center descriptors, readily accessible intrinsic property descriptors, and spin-related descriptors, all of which contribute to a profound understanding of catalytic behavior. Furthermore, multi-type descriptors that collectively determine the catalytic performance are also summarized. Finally, we discuss the future of descriptors, envisioning their potential to integrate multiple factors, broaden application scopes, and synergize with artificial intelligence for more efficient catalyst design and discovery.
描述符在电催化中发挥着至关重要的作用,因为它们可以为能量转换和储存过程的电化学性能提供宝贵的见解。通过描述符可以了解不同的催化活性,并预测更好的催化剂,而无需依赖耗时的试错方法。因此,本综合综述重点强调了关键电催化反应常用描述符的重大进展。首先,概述了几个电催化反应中涉及的基本反应过程和关键中间产物。随后,根据不同的反应和催化剂对三类描述子进行了分类和介绍。这些描述符包括 d 带中心描述符、易于获取的固有属性描述符和自旋相关描述符,它们都有助于深入理解催化行为。此外,我们还总结了共同决定催化性能的多类型描述符。最后,我们讨论了描述符的未来,展望了描述符整合多种因素、拓宽应用范围以及与人工智能协同提高催化剂设计和发现效率的潜力。
{"title":"Advancing electrocatalytic reactions through mapping key intermediates to active sites <i>via</i> descriptors.","authors":"Xiaowen Sun, Rafael B Araujo, Egon Campos Dos Santos, Yuanhua Sang, Hong Liu, Xiaowen Yu","doi":"10.1039/d3cs01130e","DOIUrl":"https://doi.org/10.1039/d3cs01130e","url":null,"abstract":"<p><p>Descriptors play a crucial role in electrocatalysis as they can provide valuable insights into the electrochemical performance of energy conversion and storage processes. They allow for the understanding of different catalytic activities and enable the prediction of better catalysts without relying on the time-consuming trial-and-error approaches. Hence, this comprehensive review focuses on highlighting the significant advancements in commonly used descriptors for critical electrocatalytic reactions. First, the fundamental reaction processes and key intermediates involved in several electrocatalytic reactions are summarized. Subsequently, three types of descriptors are classified and introduced based on different reactions and catalysts. These include d-band center descriptors, readily accessible intrinsic property descriptors, and spin-related descriptors, all of which contribute to a profound understanding of catalytic behavior. Furthermore, multi-type descriptors that collectively determine the catalytic performance are also summarized. Finally, we discuss the future of descriptors, envisioning their potential to integrate multiple factors, broaden application scopes, and synergize with artificial intelligence for more efficient catalyst design and discovery.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141416702","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Junzhi Ye, Deepika Gaur, Chenjia Mi, Zijian Chen, Iago López Fernández, Haitao Zhao, Yitong Dong, Lakshminarayana Polavarapu, Robert L Z Hoye
Colloidal semiconductor nanocrystals enable the realization and exploitation of quantum phenomena in a controlled manner, and can be scaled up for commercial uses. These materials have become important for a wide range of applications, from ultrahigh definition displays, to solar cells, quantum computing, bioimaging, optical communications, and many more. Over the last decade, lead-halide perovskite nanocrystals have rapidly gained prominence as efficient semiconductors. Although the majority of studies have focused on large nanocrystals in the weak- to intermediate-confinement regime, quantum dots (QDs) in the strongly-confined regime (with sizes smaller than the Bohr diameter, which ranges from 4-12 nm for lead-halide perovskites) offer unique opportunities, including polarized light emission and color-pure, stable luminescence in the region that is unattainable by perovskites with single-halide compositions. In this tutorial review, we bring together the latest insights into this emerging and rapidly growing area, focusing on the synthesis, steady-state optical properties (including exciton fine-structure splitting), and transient kinetics (including hot carrier cooling) of strongly-confined perovskite QDs. We also discuss recent advances in their applications, including single photon emission for quantum technologies, as well as light-emitting diodes. We finish with our perspectives on future challenges and opportunities for strongly-confined QDs, particularly around improving the control over monodispersity and stability, important fundamental questions on the photophysics, and paths forward to improve the performance of perovskite QDs in light-emitting diodes.
{"title":"Strongly-confined colloidal lead-halide perovskite quantum dots: from synthesis to applications.","authors":"Junzhi Ye, Deepika Gaur, Chenjia Mi, Zijian Chen, Iago López Fernández, Haitao Zhao, Yitong Dong, Lakshminarayana Polavarapu, Robert L Z Hoye","doi":"10.1039/d4cs00077c","DOIUrl":"https://doi.org/10.1039/d4cs00077c","url":null,"abstract":"<p><p>Colloidal semiconductor nanocrystals enable the realization and exploitation of quantum phenomena in a controlled manner, and can be scaled up for commercial uses. These materials have become important for a wide range of applications, from ultrahigh definition displays, to solar cells, quantum computing, bioimaging, optical communications, and many more. Over the last decade, lead-halide perovskite nanocrystals have rapidly gained prominence as efficient semiconductors. Although the majority of studies have focused on large nanocrystals in the weak- to intermediate-confinement regime, quantum dots (QDs) in the strongly-confined regime (with sizes smaller than the Bohr diameter, which ranges from 4-12 nm for lead-halide perovskites) offer unique opportunities, including polarized light emission and color-pure, stable luminescence in the region that is unattainable by perovskites with single-halide compositions. In this tutorial review, we bring together the latest insights into this emerging and rapidly growing area, focusing on the synthesis, steady-state optical properties (including exciton fine-structure splitting), and transient kinetics (including hot carrier cooling) of strongly-confined perovskite QDs. We also discuss recent advances in their applications, including single photon emission for quantum technologies, as well as light-emitting diodes. We finish with our perspectives on future challenges and opportunities for strongly-confined QDs, particularly around improving the control over monodispersity and stability, important fundamental questions on the photophysics, and paths forward to improve the performance of perovskite QDs in light-emitting diodes.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141416705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Oxidative degradation is a powerful method to degrade plastics into oligomers and small oxidized products. While thermal energy has been conventionally employed as an external stimulus, recent advances in photochemistry have enabled photocatalytic oxidative degradation of polymers under mild conditions. This tutorial review presents an overview of oxidative degradation, from its earliest examples to emerging strategies. This review briefly discusses the motivation and the development of thermal oxidative degradation of polymers with a focus on underlying mechanisms. Then, we will examine modern studies primarily relevant to catalytic thermal oxidative degradation and photocatalytic oxidative degradation. Lastly, we highlight some unique studies using unconventional approaches for oxidative polymer degradation, such as electrochemistry.
{"title":"Recent advances in oxidative degradation of plastics.","authors":"Sewon Oh, Erin E Stache","doi":"10.1039/d4cs00407h","DOIUrl":"https://doi.org/10.1039/d4cs00407h","url":null,"abstract":"<p><p>Oxidative degradation is a powerful method to degrade plastics into oligomers and small oxidized products. While thermal energy has been conventionally employed as an external stimulus, recent advances in photochemistry have enabled photocatalytic oxidative degradation of polymers under mild conditions. This tutorial review presents an overview of oxidative degradation, from its earliest examples to emerging strategies. This review briefly discusses the motivation and the development of thermal oxidative degradation of polymers with a focus on underlying mechanisms. Then, we will examine modern studies primarily relevant to catalytic thermal oxidative degradation and photocatalytic oxidative degradation. Lastly, we highlight some unique studies using unconventional approaches for oxidative polymer degradation, such as electrochemistry.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141329741","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Andrea Pizzi, Arun Dhaka, Roberta Beccaria and Giuseppe Resnati
The electrostatic attraction between charges of opposite signs and the repulsion between charges of the same sign are ubiquitous and influential phenomena in recognition and self-assembly processes. However, it has been recently revealed that specific attractive forces between ions with the same sign are relatively common. These forces can be strong enough to overcome the Coulomb repulsion between ions with the same sign, leading to the formation of stable anion⋯anion and cation⋯cation adducts. Hydroden bonds (HBs) are probably the best-known interaction that can effectively direct these counterintuitive assembly processes. In this review we discuss how σ-hole and π-hole bonds can break the paradigm of electrostatic repulsion between like-charges and effectively drive the self-assembly of anions into discrete as well as one-, two-, or three-dimensional adducts. σ-Hole and π-hole bonds are the attractive forces between regions of excess electron density in molecular entities (e.g., lone pairs or π bond orbitals) and regions of depleted electron density that are localized at the outer surface of bonded atoms opposite to the σ covalent bonds formed by atoms (σ-holes) and above and below the planar portions of molecular entities (π-holes). σ- and π-holes can be present on many different elements of the p and d block of the periodic table and the self-assembly processes driven by their presence can thus involve a wide diversity of mono- and di-anions. The formed homomeric and heteromeric adducts are typically stable in the solid phase and in polar solvents but metastable or unstable in the gas phase. The pivotal role of σ- and π-hole bonds in controlling anion⋯anion self-assembly is described in key biopharmacological systems and in molecular materials endowed with useful functional properties.
在识别和自组装过程中,符号相反的电荷之间的静电吸引和符号相同的电荷之间的静电排斥是无处不在、影响深远的现象。然而,最近有研究发现,同号离子之间的特殊吸引力也比较常见。这些作用力足以克服同号离子之间的库仑斥力,从而形成稳定的阴离子⋯阳离子和阳离子⋯阳离子加合物。氢键(HB)可能是最著名的相互作用,它能有效地引导这些反直觉的组装过程。在这篇综述中,我们将讨论σ-孔和π-孔键如何打破同类电荷之间的静电排斥模式,并有效地推动阴离子自组装成离散的以及一维、二维或三维的加合物、σ-孔和π-孔可能存在于元素周期表中 p 和 d 组的许多不同元素上,因此由它们的存在所驱动的自组装过程可能涉及多种单离子和二离子。所形成的同分异构体和异分异构体加合物通常在固相和极性溶剂中都很稳定,但在气相中却很不稳定。在关键的生物药理系统和具有有用功能特性的分子材料中,σ- 和 π-孔键在控制阴离子⋯阴离子自组装中发挥了关键作用。
{"title":"Anion⋯anion self-assembly under the control of σ- and π-hole bonds","authors":"Andrea Pizzi, Arun Dhaka, Roberta Beccaria and Giuseppe Resnati","doi":"10.1039/D3CS00479A","DOIUrl":"10.1039/D3CS00479A","url":null,"abstract":"<p >The electrostatic attraction between charges of opposite signs and the repulsion between charges of the same sign are ubiquitous and influential phenomena in recognition and self-assembly processes. However, it has been recently revealed that specific attractive forces between ions with the same sign are relatively common. These forces can be strong enough to overcome the Coulomb repulsion between ions with the same sign, leading to the formation of stable anion⋯anion and cation⋯cation adducts. Hydroden bonds (HBs) are probably the best-known interaction that can effectively direct these counterintuitive assembly processes. In this review we discuss how σ-hole and π-hole bonds can break the paradigm of electrostatic repulsion between like-charges and effectively drive the self-assembly of anions into discrete as well as one-, two-, or three-dimensional adducts. σ-Hole and π-hole bonds are the attractive forces between regions of excess electron density in molecular entities (<em>e.g.</em>, lone pairs or π bond orbitals) and regions of depleted electron density that are localized at the outer surface of bonded atoms opposite to the σ covalent bonds formed by atoms (σ-holes) and above and below the planar portions of molecular entities (π-holes). σ- and π-holes can be present on many different elements of the p and d block of the periodic table and the self-assembly processes driven by their presence can thus involve a wide diversity of mono- and di-anions. The formed homomeric and heteromeric adducts are typically stable in the solid phase and in polar solvents but metastable or unstable in the gas phase. The pivotal role of σ- and π-hole bonds in controlling anion⋯anion self-assembly is described in key biopharmacological systems and in molecular materials endowed with useful functional properties.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":40.4,"publicationDate":"2024-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d3cs00479a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141309678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jianhua Han, Han Xu, Sri Harish Kumar Paleti, Anirudh Sharma, Derya Baran
Over the past decades, the field of organic solar cells (OSCs) has witnessed a significant evolution in materials chemistry, which has resulted in a remarkable enhancement of device performance, achieving efficiencies of over 19%. The photoactive layer materials in OSCs play a crucial role in light absorption, charge generation, transport and stability. To facilitate the scale-up of OSCs, it is imperative to address the photostability of these electron acceptor and donor materials, as their photochemical degradation process remains a challenge during the photo-to-electric conversion. In this review, we present an overview of the development of electron acceptor and donor materials, emphasizing the crucial aspects of their chemical stability behavior that are linked to the photostability of OSCs. Throughout each section, we highlight the photochemical degradation pathways for electron acceptor and donor materials, and their link to device degradation. We also discuss the existing interdisciplinary challenges and obstacles that impede the development of photostable materials. Finally, we offer insights into strategies aimed at enhancing photochemical stability and discuss future directions for developing photostable photo-active layers, facilitating the commercialization of OSCs.
{"title":"Understanding photochemical degradation mechanisms in photoactive layer materials for organic solar cells.","authors":"Jianhua Han, Han Xu, Sri Harish Kumar Paleti, Anirudh Sharma, Derya Baran","doi":"10.1039/d4cs00132j","DOIUrl":"https://doi.org/10.1039/d4cs00132j","url":null,"abstract":"<p><p>Over the past decades, the field of organic solar cells (OSCs) has witnessed a significant evolution in materials chemistry, which has resulted in a remarkable enhancement of device performance, achieving efficiencies of over 19%. The photoactive layer materials in OSCs play a crucial role in light absorption, charge generation, transport and stability. To facilitate the scale-up of OSCs, it is imperative to address the photostability of these electron acceptor and donor materials, as their photochemical degradation process remains a challenge during the photo-to-electric conversion. In this review, we present an overview of the development of electron acceptor and donor materials, emphasizing the crucial aspects of their chemical stability behavior that are linked to the photostability of OSCs. Throughout each section, we highlight the photochemical degradation pathways for electron acceptor and donor materials, and their link to device degradation. We also discuss the existing interdisciplinary challenges and obstacles that impede the development of photostable materials. Finally, we offer insights into strategies aimed at enhancing photochemical stability and discuss future directions for developing photostable photo-active layers, facilitating the commercialization of OSCs.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141309679","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yi Lu, Marina Mehling, Siqi Huan, Long Bai, Orlando J Rojas
Nanocellulose is not only a renewable material but also brings functions that are opening new technological opportunities. Here we discuss a special subset of this material, in its fibrillated form, which is produced by aerobic microorganisms, namely, bacterial nanocellulose (BNC). BNC offers distinct advantages over plant-derived counterparts, including high purity and high degree of polymerization as well as crystallinity, strength, and water-holding capacity, among others. More remarkably, beyond classical fermentative protocols, it is possible to grow BNC on non-planar interfaces, opening new possibilities in the assembly of advanced bottom-up structures. In this review, we discuss the recent advances in the area of BNC-based biofabrication of three-dimensional (3D) designs by following solid- and soft-material templating. These methods are shown as suitable platforms to achieve bioadaptive constructs comprising highly interlocked biofilms that can be tailored with precise control over nanoscale morphological features. BNC-based biofabrication opens applications that are not possible by using traditional manufacturing routes, including direct ink writing of hydrogels. This review emphasizes the critical contributions of microbiology, colloid and surface science, as well as additive manufacturing in achieving bioadaptive designs from living matter. The future impact of BNC biofabrication is expected to take advantage of material and energy integration, residue utilization, circularity and social latitudes. Leveraging existing infrastructure, the scaleup of biofabrication routes will contribute to a new generation of advanced materials rooted in exciting synergies that combine biology, chemistry, engineering and material sciences.
{"title":"Biofabrication with microbial cellulose: from bioadaptive designs to living materials.","authors":"Yi Lu, Marina Mehling, Siqi Huan, Long Bai, Orlando J Rojas","doi":"10.1039/d3cs00641g","DOIUrl":"https://doi.org/10.1039/d3cs00641g","url":null,"abstract":"<p><p>Nanocellulose is not only a renewable material but also brings functions that are opening new technological opportunities. Here we discuss a special subset of this material, in its fibrillated form, which is produced by aerobic microorganisms, namely, bacterial nanocellulose (BNC). BNC offers distinct advantages over plant-derived counterparts, including high purity and high degree of polymerization as well as crystallinity, strength, and water-holding capacity, among others. More remarkably, beyond classical fermentative protocols, it is possible to grow BNC on non-planar interfaces, opening new possibilities in the assembly of advanced bottom-up structures. In this review, we discuss the recent advances in the area of BNC-based biofabrication of three-dimensional (3D) designs by following solid- and soft-material templating. These methods are shown as suitable platforms to achieve bioadaptive constructs comprising highly interlocked biofilms that can be tailored with precise control over nanoscale morphological features. BNC-based biofabrication opens applications that are not possible by using traditional manufacturing routes, including direct ink writing of hydrogels. This review emphasizes the critical contributions of microbiology, colloid and surface science, as well as additive manufacturing in achieving bioadaptive designs from living matter. The future impact of BNC biofabrication is expected to take advantage of material and energy integration, residue utilization, circularity and social latitudes. Leveraging existing infrastructure, the scaleup of biofabrication routes will contribute to a new generation of advanced materials rooted in exciting synergies that combine biology, chemistry, engineering and material sciences.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141304914","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Seawater electrolysis for the production of fuels and chemicals involved in onshore and offshore plants powered by renewable energies offers a promising avenue and unique advantages for energy and environmental sustainability. Nevertheless, seawater electrolysis presents long-term challenges and issues, such as complex composition, potential side reactions, deposition of and poisoning by microorganisms and metal ions, as well as corrosion, thus hindering the rapid development of seawater electrolysis technology. This review focuses on the production of value-added fuels (hydrogen and beyond) and fine chemicals through seawater electrolysis, as a promising step towards sustainable energy development and carbon neutrality. The principle of seawater electrolysis and related challenges are first introduced, and the redox reaction mechanisms of fuels and chemicals are summarized. Strategies for operating anodes and cathodes including the development and application of chloride- and impurity-resistant electrocatalysts/membranes are reviewed. We comprehensively summarize the production of fuels and chemicals (hydrogen, carbon monoxide, sulfur, ammonia, etc.) at the cathode and anode via seawater electrolysis, and propose other potential strategies for co-producing fine chemicals, even sophisticated and electronic chemicals. Seawater electrolysis can drive the oxidation and upgrading of industrial pollutants or natural organics into value-added chemicals or degrade them into harmless substances, which would be meaningful for environmental protection. Finally, the perspective and prospects are outlined to address the challenges and expand the application of seawater electrolysis.
{"title":"Seawater electrolysis for fuels and chemicals production: fundamentals, achievements, and perspectives.","authors":"Lin Chen, Chang Yu, Junting Dong, Yingnan Han, Hongling Huang, Wenbin Li, Yafang Zhang, Xinyi Tan, Jieshan Qiu","doi":"10.1039/d3cs00822c","DOIUrl":"https://doi.org/10.1039/d3cs00822c","url":null,"abstract":"<p><p>Seawater electrolysis for the production of fuels and chemicals involved in onshore and offshore plants powered by renewable energies offers a promising avenue and unique advantages for energy and environmental sustainability. Nevertheless, seawater electrolysis presents long-term challenges and issues, such as complex composition, potential side reactions, deposition of and poisoning by microorganisms and metal ions, as well as corrosion, thus hindering the rapid development of seawater electrolysis technology. This review focuses on the production of value-added fuels (hydrogen and beyond) and fine chemicals through seawater electrolysis, as a promising step towards sustainable energy development and carbon neutrality. The principle of seawater electrolysis and related challenges are first introduced, and the redox reaction mechanisms of fuels and chemicals are summarized. Strategies for operating anodes and cathodes including the development and application of chloride- and impurity-resistant electrocatalysts/membranes are reviewed. We comprehensively summarize the production of fuels and chemicals (hydrogen, carbon monoxide, sulfur, ammonia, <i>etc.</i>) at the cathode and anode <i>via</i> seawater electrolysis, and propose other potential strategies for co-producing fine chemicals, even sophisticated and electronic chemicals. Seawater electrolysis can drive the oxidation and upgrading of industrial pollutants or natural organics into value-added chemicals or degrade them into harmless substances, which would be meaningful for environmental protection. Finally, the perspective and prospects are outlined to address the challenges and expand the application of seawater electrolysis.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":null,"pages":null},"PeriodicalIF":46.2,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141295142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}