Pub Date : 2025-11-24DOI: 10.1021/acs.chemrev.5c00332
David Reber*, , , Zhiyu Wang, , , Kiana Amini, , , Yan Jing, , , Julia Lorenzetti, , , Kang Xu, , , Abhishek Khetan, , and , Qing Wang,
This review provides a foundational understanding of solubility to support researchers in navigating challenges in battery electrolyte development. We survey recent strategies aimed at controlling, and typically maximizing, solubility in electrochemical systems, with a focus on redox flow and metal-ion batteries. The review begins with an accessible overview of solubility concepts, methods for accurately determining solubility for battery-relevant materials, and solubility prediction. We then discuss how solubility can be tuned by modifying the electrolyte solution structure or by tailoring the molecular structure of the active material itself, and we examine emerging strategies to decouple electrolyte capacity from solubility in flow batteries. In the context of metal and metal-ion batteries, we highlight the role of solvation structures in concentrated electrolytes and their influence on both bulk and interfacial properties. Finally, trade-offs associated with high-concentration formulations, such as increased viscosity and reduced ionic conductivity, are considered in light of their impact on practical deployment. We conclude with a forward-looking perspective on solubility as a central design parameter in battery electrolyte research.
{"title":"Solubility Challenges in Battery Electrolytes","authors":"David Reber*, , , Zhiyu Wang, , , Kiana Amini, , , Yan Jing, , , Julia Lorenzetti, , , Kang Xu, , , Abhishek Khetan, , and , Qing Wang, ","doi":"10.1021/acs.chemrev.5c00332","DOIUrl":"10.1021/acs.chemrev.5c00332","url":null,"abstract":"<p >This review provides a foundational understanding of solubility to support researchers in navigating challenges in battery electrolyte development. We survey recent strategies aimed at controlling, and typically maximizing, solubility in electrochemical systems, with a focus on redox flow and metal-ion batteries. The review begins with an accessible overview of solubility concepts, methods for accurately determining solubility for battery-relevant materials, and solubility prediction. We then discuss how solubility can be tuned by modifying the electrolyte solution structure or by tailoring the molecular structure of the active material itself, and we examine emerging strategies to decouple electrolyte capacity from solubility in flow batteries. In the context of metal and metal-ion batteries, we highlight the role of solvation structures in concentrated electrolytes and their influence on both bulk and interfacial properties. Finally, trade-offs associated with high-concentration formulations, such as increased viscosity and reduced ionic conductivity, are considered in light of their impact on practical deployment. We conclude with a forward-looking perspective on solubility as a central design parameter in battery electrolyte research.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"125 23","pages":"11216–11259"},"PeriodicalIF":55.8,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145593878","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}
Pub Date : 2025-11-19DOI: 10.1021/acs.chemrev.5c00658
Jie Ye, Wenzhi Gu, Jing Hu, Li Chen, Chaohui Yang, Jiangtao Gao, Shungui Zhou
Semiartificial photosynthesis has witnessed remarkable progress over the past decade, driven by the integration of diverse biological systems with synthetic materials, ushering in the first generation of biohybrid platforms (Biohybrids 1.0). While previous reviews have extensively examined whole-cell biohybrid systems and the fundamental mechanisms underlying solar-to-chemical energy conversion, a critical knowledge gap remains in the rational optimization of their three core components: photosensitizers, microbial partners, and solar energy input. These interdependent elements collectively determine the efficiency, stability, and scalability of biohybrid platforms. To address this gap, this review offers a comprehensive and structured overview of multidisciplinary strategies for the development of next-generation biohybrid platforms (Biohybrids 2.0). It highlights recent advances in photosensitizer design, microbial selection and engineering, energy sources and conversion strategies, interface control and optimization, and state-of-the-art characterization methodologies, while providing a comprehensive summary of a diverse and expanding range of emerging applications. The review also offers a critical appraisal of current limitations and proposes forward-looking research directions that may enable transformative progress toward Biohybrids 3.0. Altogether, this integrative perspective outlines a coherent framework for the rational design of robust, efficient, and application-ready semiartificial photosynthetic systems for real-world and industrial-scale deployment.
{"title":"Toward Next-Generation Semiartificial Photosynthesis: Multidisciplinary Engineering of Biohybrid Systems","authors":"Jie Ye, Wenzhi Gu, Jing Hu, Li Chen, Chaohui Yang, Jiangtao Gao, Shungui Zhou","doi":"10.1021/acs.chemrev.5c00658","DOIUrl":"https://doi.org/10.1021/acs.chemrev.5c00658","url":null,"abstract":"Semiartificial photosynthesis has witnessed remarkable progress over the past decade, driven by the integration of diverse biological systems with synthetic materials, ushering in the first generation of biohybrid platforms (Biohybrids 1.0). While previous reviews have extensively examined whole-cell biohybrid systems and the fundamental mechanisms underlying solar-to-chemical energy conversion, a critical knowledge gap remains in the rational optimization of their three core components: photosensitizers, microbial partners, and solar energy input. These interdependent elements collectively determine the efficiency, stability, and scalability of biohybrid platforms. To address this gap, this review offers a comprehensive and structured overview of multidisciplinary strategies for the development of next-generation biohybrid platforms (Biohybrids 2.0). It highlights recent advances in photosensitizer design, microbial selection and engineering, energy sources and conversion strategies, interface control and optimization, and state-of-the-art characterization methodologies, while providing a comprehensive summary of a diverse and expanding range of emerging applications. The review also offers a critical appraisal of current limitations and proposes forward-looking research directions that may enable transformative progress toward Biohybrids 3.0. Altogether, this integrative perspective outlines a coherent framework for the rational design of robust, efficient, and application-ready semiartificial photosynthetic systems for real-world and industrial-scale deployment.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"98 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145546360","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}
Pub Date : 2025-11-18DOI: 10.1021/acs.chemrev.5c00659
Yifei Xu, Johanna M. Galloway, L. Jorin Hasselt, Fiona C. Meldrum
This review focuses on an important but under-explored biogenic strategy used to control biomineralization processes─confinement─where compartmentalization is fundamental to the organization and function of all organisms. Biominerals combine the functionality of inorganic and organic solid-state materials and are constructed under precise biological control. Often exhibiting desirable properties, such as high strength, toughness, and complex morphologies that surpass those of synthetic materials synthesized under harsher conditions, biomineral formation processes are widely studied. Here we demonstrate the vital role that confinement plays in defining the key structural characteristics of biominerals and in controlling their mechanisms of formation. These range from well-accepted functions, such as stabilizing amorphous phases, isolating the mineralization site, and controlling morphologies, to more speculative roles, including controlling crystal nucleation, orientation and polymorphism. Examples from a range of organisms, mineral types, and length scales are provided, and further insight into potential biogenic mechanisms is gained through comparison with crystallization in complementary confined synthetic systems. Further opportunities for exploring confinement effects in biomineralization systems are discussed throughout, where these will ultimately act as an inspiration for the synthesis of sustainable materials, for medical innovations, as well as providing insights into evolution and environmental change.
{"title":"The Role of Confinement in Biomineralization","authors":"Yifei Xu, Johanna M. Galloway, L. Jorin Hasselt, Fiona C. Meldrum","doi":"10.1021/acs.chemrev.5c00659","DOIUrl":"https://doi.org/10.1021/acs.chemrev.5c00659","url":null,"abstract":"This review focuses on an important but under-explored biogenic strategy used to control biomineralization processes─confinement─where compartmentalization is fundamental to the organization and function of all organisms. Biominerals combine the functionality of inorganic and organic solid-state materials and are constructed under precise biological control. Often exhibiting desirable properties, such as high strength, toughness, and complex morphologies that surpass those of synthetic materials synthesized under harsher conditions, biomineral formation processes are widely studied. Here we demonstrate the vital role that confinement plays in defining the key structural characteristics of biominerals and in controlling their mechanisms of formation. These range from well-accepted functions, such as stabilizing amorphous phases, isolating the mineralization site, and controlling morphologies, to more speculative roles, including controlling crystal nucleation, orientation and polymorphism. Examples from a range of organisms, mineral types, and length scales are provided, and further insight into potential biogenic mechanisms is gained through comparison with crystallization in complementary confined synthetic systems. Further opportunities for exploring confinement effects in biomineralization systems are discussed throughout, where these will ultimately act as an inspiration for the synthesis of sustainable materials, for medical innovations, as well as providing insights into evolution and environmental change.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"155 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536292","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}
Pub Date : 2025-11-18DOI: 10.1021/acs.chemrev.5c00763
David Rickard
Research into tetragonal FeSm, the synthetic equivalent of the mineral mackinawite, is currently at the frontiers of theoretical and applied chemistry. FeSm is stoichiometric and crystallizes with a structure dominated by Fe–Fe layers. The familiar black, nanoparticulate precipitate develops from aqueous FeS clusters and displays varying initial compositions. Particle growth and crystallization are through oriented attachment of FeS nanoplates. Conflicting magnetic properties of FeSm result from itinerant Fe d-electrons in the ground state displaying some localization experimentally. It is highly sensitive to the method of synthesis and this has led to widespread irreproducible, and often conflicting, results. At the same time this sensitivity offers the opportunity to synthesize FeSm varieties with technologically valuable properties. FeSm displays unconventional superconductivity (Tc ∼ 5K) derived from spatial anisotropy of electron pairs. Exotic compounds can be inserted in the vdW gap between the FeS layers giving rise to a spectrum of interlayered compounds. FeSm can be highly efficient in sequestering a large array of environmentally deleterious inorganic and organic compounds including halogenated hydrocarbons. However, FeSm nanoparticles are genotoxic and this needs to be further investigated before they are widely distributed in the environment or used for medical purposes.
{"title":"The Chemistry of Tetragonal FeS","authors":"David Rickard","doi":"10.1021/acs.chemrev.5c00763","DOIUrl":"https://doi.org/10.1021/acs.chemrev.5c00763","url":null,"abstract":"Research into tetragonal FeS<sub>m</sub>, the synthetic equivalent of the mineral mackinawite, is currently at the frontiers of theoretical and applied chemistry. FeS<sub>m</sub> is stoichiometric and crystallizes with a structure dominated by Fe–Fe layers. The familiar black, nanoparticulate precipitate develops from aqueous FeS clusters and displays varying initial compositions. Particle growth and crystallization are through oriented attachment of FeS nanoplates. Conflicting magnetic properties of FeS<sub>m</sub> result from itinerant Fe d-electrons in the ground state displaying some localization experimentally. It is highly sensitive to the method of synthesis and this has led to widespread irreproducible, and often conflicting, results. At the same time this sensitivity offers the opportunity to synthesize FeS<sub>m</sub> varieties with technologically valuable properties. FeS<sub>m</sub> displays unconventional superconductivity (<i>T</i><sub>c</sub> ∼ 5K) derived from spatial anisotropy of electron pairs. Exotic compounds can be inserted in the vdW gap between the FeS layers giving rise to a spectrum of interlayered compounds. FeS<sub>m</sub> can be highly efficient in sequestering a large array of environmentally deleterious inorganic and organic compounds including halogenated hydrocarbons. However, FeS<sub>m</sub> nanoparticles are genotoxic and this needs to be further investigated before they are widely distributed in the environment or used for medical purposes.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"6 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536293","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}
Pub Date : 2025-11-17DOI: 10.1021/acs.chemrev.5c00528
Pei-Yi Chen, and , Eric P. Skaar*,
Heme is an essential molecule required for critical biochemical processes in most vertebrates and bacteria. During infections, vertebrate hosts sequester heme away from invading pathogens, a process known as nutritional immunity, driving bacteria to evolve diverse mechanisms to evade this immunity and cause diseases. This review explores the functions of heme at the host–pathogen interface. We discuss the multifaceted roles of heme in bacterial pathogenesis and the potential for heme-targeting antimicrobial therapies. Beyond serving as a source of iron in the host environment, where iron bioavailability is limited, heme contributes to the structural stability and enzymatic functions of hemoproteins. We examine the regulatory mechanisms governing bacterial heme homeostasis in the host environment including sensing, detoxification, acquisition, utilization, and degradation pathways. Understanding how heme influences bacterial survival and virulence can lead to the development of novel therapeutic strategies that target the various essential and conserved mechanisms of heme homeostasis in bacterial pathogens. Given the rising challenge of antibiotic resistance, heme-based therapeutic interventions are promising strategies for the treatment of bacterial infections.
{"title":"Heme in Bacterial Pathogenesis and as an Antimicrobial Target","authors":"Pei-Yi Chen, and , Eric P. Skaar*, ","doi":"10.1021/acs.chemrev.5c00528","DOIUrl":"10.1021/acs.chemrev.5c00528","url":null,"abstract":"<p >Heme is an essential molecule required for critical biochemical processes in most vertebrates and bacteria. During infections, vertebrate hosts sequester heme away from invading pathogens, a process known as nutritional immunity, driving bacteria to evolve diverse mechanisms to evade this immunity and cause diseases. This review explores the functions of heme at the host–pathogen interface. We discuss the multifaceted roles of heme in bacterial pathogenesis and the potential for heme-targeting antimicrobial therapies. Beyond serving as a source of iron in the host environment, where iron bioavailability is limited, heme contributes to the structural stability and enzymatic functions of hemoproteins. We examine the regulatory mechanisms governing bacterial heme homeostasis in the host environment including sensing, detoxification, acquisition, utilization, and degradation pathways. Understanding how heme influences bacterial survival and virulence can lead to the development of novel therapeutic strategies that target the various essential and conserved mechanisms of heme homeostasis in bacterial pathogens. Given the rising challenge of antibiotic resistance, heme-based therapeutic interventions are promising strategies for the treatment of bacterial infections.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"125 22","pages":"11120–11144"},"PeriodicalIF":55.8,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.chemrev.5c00528","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536325","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}
Pub Date : 2025-11-13DOI: 10.1021/acs.chemrev.5c00377
Graeme Puxty*, , , Marcel Maeder, , and , Thomas Moore,
Point source carbon capture is a technology that has been developed to separate carbon dioxide (CO2) from gas mixtures prior to emission to the atmosphere. It is considered a crucial technology to manage CO2 emissions from fossil fuel-based heat and power and industrial processes as part of emissions reduction strategies. The most mature technology is reactive chemical absorption using aqueous amines, with other options emerging. In this review we have described the chemistry of liquid-based reactive chemical absorption and examined the current state-of-the-art in terms of the molecules being investigated. We have also highlighted the critical properties relevant for an absorbent to be effective for carbon capture. The chemical and physical properties have also been considered in terms of how they influence process performance, both positively and negatively, with emphasis on the multifaceted nature of this relationship and the importance of understanding both the chemistry and chemical engineering when endeavoring to make improvements.
{"title":"The Chemistry and Thermodynamics of Point Source CO2 Capture by Liquid Chemical Absorption and Its Impact on Process Performance","authors":"Graeme Puxty*, , , Marcel Maeder, , and , Thomas Moore, ","doi":"10.1021/acs.chemrev.5c00377","DOIUrl":"10.1021/acs.chemrev.5c00377","url":null,"abstract":"<p >Point source carbon capture is a technology that has been developed to separate carbon dioxide (CO<sub>2</sub>) from gas mixtures prior to emission to the atmosphere. It is considered a crucial technology to manage CO<sub>2</sub> emissions from fossil fuel-based heat and power and industrial processes as part of emissions reduction strategies. The most mature technology is reactive chemical absorption using aqueous amines, with other options emerging. In this review we have described the chemistry of liquid-based reactive chemical absorption and examined the current state-of-the-art in terms of the molecules being investigated. We have also highlighted the critical properties relevant for an absorbent to be effective for carbon capture. The chemical and physical properties have also been considered in terms of how they influence process performance, both positively and negatively, with emphasis on the multifaceted nature of this relationship and the importance of understanding both the chemistry and chemical engineering when endeavoring to make improvements.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"125 22","pages":"10956–10993"},"PeriodicalIF":55.8,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.chemrev.5c00377","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145498232","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}
Pub Date : 2025-11-07DOI: 10.1021/acs.chemrev.5c00430
Ruchika Ojha, , , Christian G. Hartinger, , , Alan M. Bond, , , Ingo Ott, , , Magdalena Plebanski, , , Hubert Schmidbaur, , and , Suresh K. Bhargava*,
Transition metal complexes featuring unusual oxidation states represent an exciting frontier in inorganic chemistry. This review surveys the unusual oxidation states of two biologically important metals, platinum (PtI and PtIII) and gold (AuII), examining their electronic structures, bonding characteristics, and biomedical relevance, among other features. Emphasis is placed on synthetic strategies, redox behavior, and factors influencing their stability and stabilization. PtIII complexes can potentially offer an alternative to the traditional PtII/IV anticancer chemotherapy framework and be an intermediate in PtII/IV redox chemistry. Indeed, the PtIII-based platinum blues have been widely investigated as anticancer agents soon after the landmark discovery of cisplatin as a cancer chemotherapeutic. AuII complexes are less explored for their biological properties but may be intermediates in AuI/III redox chemistry and offer an alternative pathway to gold-based chemotherapeutics. We outline current challenges and future directions in this evolving field, where fundamental chemistry meets therapeutic innovation.
{"title":"Platinum and Gold Complexes with Unusual Oxidation States and Their Potential Role in Anticancer and Therapeutic Modalities","authors":"Ruchika Ojha, , , Christian G. Hartinger, , , Alan M. Bond, , , Ingo Ott, , , Magdalena Plebanski, , , Hubert Schmidbaur, , and , Suresh K. Bhargava*, ","doi":"10.1021/acs.chemrev.5c00430","DOIUrl":"10.1021/acs.chemrev.5c00430","url":null,"abstract":"<p >Transition metal complexes featuring unusual oxidation states represent an exciting frontier in inorganic chemistry. This review surveys the unusual oxidation states of two biologically important metals, platinum (Pt<sup>I</sup> and Pt<sup>III</sup>) and gold (Au<sup>II</sup>), examining their electronic structures, bonding characteristics, and biomedical relevance, among other features. Emphasis is placed on synthetic strategies, redox behavior, and factors influencing their stability and stabilization. Pt<sup>III</sup> complexes can potentially offer an alternative to the traditional Pt<sup>II/IV</sup> anticancer chemotherapy framework and be an intermediate in Pt<sup>II/IV</sup> redox chemistry. Indeed, the Pt<sup>III</sup>-based platinum blues have been widely investigated as anticancer agents soon after the landmark discovery of cisplatin as a cancer chemotherapeutic. Au<sup>II</sup> complexes are less explored for their biological properties but may be intermediates in Au<sup>I/III</sup> redox chemistry and offer an alternative pathway to gold-based chemotherapeutics. We outline current challenges and future directions in this evolving field, where fundamental chemistry meets therapeutic innovation.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"125 22","pages":"10994–11031"},"PeriodicalIF":55.8,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145455208","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}
High-energy-density all-solid-state lithium batteries (ASSLBs) require cathodes with exceptional mechanical integrity, interfacial compatibility, and long-term electrochemical stability. Single-crystal (SC) layered oxides, distinguished from polycrystalline (PC) counterparts by their grain-boundary-free architecture and crystallographic uniformity, exhibit enhanced structural and interfacial stability while providing an ideal model system for decoupling electro-chemo-mechanical interactions. These characteristics enable precise investigation of facet-dependent transport, reaction kinetics, and degradation pathways─insights that can inform the design of both SC and advanced PC cathodes. In this review, we examine the anisotropic lithium transport, mechanical responses, and interfacial behaviors of SC cathodes, and compare them systematically with PCs to clarify how microstructural differences influence performance in ASSLBs. We further summarize advances in intrinsic material optimization, interfacial engineering, and composite electrode architectures, alongside state-of-the-art characterization and modeling tools for probing degradation mechanisms and coupling effects. Finally, we outline key challenges and research directions to accelerate the practical deployment of SC cathodes in next-generation high-energy-density ASSLBs.
{"title":"Well-Defined Single-Crystal Layered Oxide Cathodes for High-Performance All-Solid-State Lithium Batteries","authors":"Ruqin Ma, , , Siyuan Pan, , , Hanyan Wu, , , Yuxi Deng, , , Yuqi Wu, , , Yu Luo, , , Ying Lin, , , Qin Wang, , , Pengzhan Chen, , , Zhengliang Gong, , and , Yong Yang*, ","doi":"10.1021/acs.chemrev.5c00320","DOIUrl":"10.1021/acs.chemrev.5c00320","url":null,"abstract":"<p >High-energy-density all-solid-state lithium batteries (ASSLBs) require cathodes with exceptional mechanical integrity, interfacial compatibility, and long-term electrochemical stability. Single-crystal (SC) layered oxides, distinguished from polycrystalline (PC) counterparts by their grain-boundary-free architecture and crystallographic uniformity, exhibit enhanced structural and interfacial stability while providing an ideal model system for decoupling electro-chemo-mechanical interactions. These characteristics enable precise investigation of facet-dependent transport, reaction kinetics, and degradation pathways─insights that can inform the design of both SC and advanced PC cathodes. In this review, we examine the anisotropic lithium transport, mechanical responses, and interfacial behaviors of SC cathodes, and compare them systematically with PCs to clarify how microstructural differences influence performance in ASSLBs. We further summarize advances in intrinsic material optimization, interfacial engineering, and composite electrode architectures, alongside state-of-the-art characterization and modeling tools for probing degradation mechanisms and coupling effects. Finally, we outline key challenges and research directions to accelerate the practical deployment of SC cathodes in next-generation high-energy-density ASSLBs.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"125 22","pages":"10802–10875"},"PeriodicalIF":55.8,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145455207","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}
Ionic liquids (ILs) have emerged as highly tunable sorbents and membranes for gas separation, especially in the purification of CO2-containing gas streams such as air, natural gas, biogas, and syngas. Their negligible volatility, high thermal stability, and chemical versatility position them as promising alternatives to conventional amine and alkaline metal derivative-based systems, effectively addressing key challenges such as volatility, stability, and high regeneration energy. This Review explores IL-derived systems for CO2-related gas separation across dense, porous, and supported categories. At the dense liquid level, we discuss strategies for tailoring IL properties to optimize CO2 sorption, focusing on the correlation between IL-CO2 interaction strength, uptake capacity, and regeneration energy. Key advancements in carbon capture, including amino-functionalized (AILs) and superbase-derived ILs (SILs), are highlighted, along with strategies such as chemical structure engineering, multiple binding site integration, alternative driving force exploration, and stability enhancement. Then, the porous liquids (PLs) scale focuses on the emerging field integrating IL properties with permanent porosity engineering, spanning ultramicropores (<5 Å) to macropores (around 100 nm). These innovations improve gas uptake capacity, accelerate transport kinetics, introduce the gating effect, and enable the coexistence of active sites with antagonistic properties within a single IL medium. At the supported IL scale, the discussion shifts to IL- and ionic pair-modified sorbents and membranes, emphasizing the modulation of cations and anions, confinement effects from porous supports, and the IL–interface interaction to enhance CO2 separation performance, particularly in diluted gas streams. Beyond separation, this Review highlights IL-based integrated processes for CO2 capture and conversion into value-added chemicals via thermocatalytic, electrocatalytic, and photocatalytic pathways. At each scale, advanced computational and experimental tools for IL design are also discussed, providing insights into stability enhancement, sorption efficiency, and process integration. The Review concludes by addressing existing challenges and outlining future directions for IL-driven innovations in gas separation technologies.
{"title":"Frontiers of Ionic Liquids in Carbon Dioxide Separation and Valorization","authors":"Liqi Qiu, , , Errui Li, , , Tian Ke, , , Qingju Wang, , , Yujing Tong, , , Bo Li, , , Hongjun Liu, , , De-en Jiang*, , , Shannon M. Mahurin, , , Zhenzhen Yang*, , and , Sheng Dai*, ","doi":"10.1021/acs.chemrev.5c00329","DOIUrl":"10.1021/acs.chemrev.5c00329","url":null,"abstract":"<p >Ionic liquids (ILs) have emerged as highly tunable sorbents and membranes for gas separation, especially in the purification of CO<sub>2</sub>-containing gas streams such as air, natural gas, biogas, and syngas. Their negligible volatility, high thermal stability, and chemical versatility position them as promising alternatives to conventional amine and alkaline metal derivative-based systems, effectively addressing key challenges such as volatility, stability, and high regeneration energy. This Review explores IL-derived systems for CO<sub>2</sub>-related gas separation across dense, porous, and supported categories. At the dense liquid level, we discuss strategies for tailoring IL properties to optimize CO<sub>2</sub> sorption, focusing on the correlation between IL-CO<sub>2</sub> interaction strength, uptake capacity, and regeneration energy. Key advancements in carbon capture, including amino-functionalized (AILs) and superbase-derived ILs (SILs), are highlighted, along with strategies such as chemical structure engineering, multiple binding site integration, alternative driving force exploration, and stability enhancement. Then, the porous liquids (PLs) scale focuses on the emerging field integrating IL properties with permanent porosity engineering, spanning ultramicropores (<5 Å) to macropores (around 100 nm). These innovations improve gas uptake capacity, accelerate transport kinetics, introduce the gating effect, and enable the coexistence of active sites with antagonistic properties within a single IL medium. At the supported IL scale, the discussion shifts to IL- and ionic pair-modified sorbents and membranes, emphasizing the modulation of cations and anions, confinement effects from porous supports, and the IL–interface interaction to enhance CO<sub>2</sub> separation performance, particularly in diluted gas streams. Beyond separation, this Review highlights IL-based integrated processes for CO<sub>2</sub> capture and conversion into value-added chemicals via thermocatalytic, electrocatalytic, and photocatalytic pathways. At each scale, advanced computational and experimental tools for IL design are also discussed, providing insights into stability enhancement, sorption efficiency, and process integration. The Review concludes by addressing existing challenges and outlining future directions for IL-driven innovations in gas separation technologies.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"125 22","pages":"10876–10955"},"PeriodicalIF":55.8,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145447983","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}
Pub Date : 2025-11-04DOI: 10.1021/acs.chemrev.5c00569
Zachary A. VanOrman*, , , Colette M. Sullivan, , , Charles W. Yang, , , Jussi Isokuortti, , and , Lea Nienhaus*,
Photon upconversion, the process of converting low-energy photons to higher energy ones, shows promise for applications in solar energy, photocatalysis, biomedicine, and additive manufacturing. In triplet–triplet annihilation (TTA), incident low-energy photons populate metastable spin-triplet states that annihilate to generate high-energy emissive spin-singlet states. Thus, TTA-based photon upconversion (TTA-UC) can operate efficiently under incoherent and low-intensity excitation, such as sunlight. In this Review, we discuss the recent emergence of halide perovskite-based materials as potent triplet sensitizers for a variety of applications. Due to their strong and tunable absorption and high defect tolerance, perovskite materials ranging from nanocrystalline to bulk semiconductors enable efficient TTA-UC in both solution and solid-state systems. After introducing the TTA-UC process and giving a brief overview of its beginnings, we first consider TTA-UC systems based on perovskite nanocrystals and low-dimensional perovskite-inspired materials and the achievements that have been made in those areas. We then focus on the mechanism of bulk perovskite-sensitized TTA-UC, the impact the underlying structure holds, and review the current challenges in perovskite-sensitized solid-state UC and outline future research directions to unlock the full potential of TTA-UC in practical applications.
{"title":"Lead the Way: Halide Perovskites as Next-Generation Triplet Sensitizers for Photon Upconversion","authors":"Zachary A. VanOrman*, , , Colette M. Sullivan, , , Charles W. Yang, , , Jussi Isokuortti, , and , Lea Nienhaus*, ","doi":"10.1021/acs.chemrev.5c00569","DOIUrl":"10.1021/acs.chemrev.5c00569","url":null,"abstract":"<p >Photon upconversion, the process of converting low-energy photons to higher energy ones, shows promise for applications in solar energy, photocatalysis, biomedicine, and additive manufacturing. In triplet–triplet annihilation (TTA), incident low-energy photons populate metastable spin-triplet states that annihilate to generate high-energy emissive spin-singlet states. Thus, TTA-based photon upconversion (TTA-UC) can operate efficiently under incoherent and low-intensity excitation, such as sunlight. In this Review, we discuss the recent emergence of halide perovskite-based materials as potent triplet sensitizers for a variety of applications. Due to their strong and tunable absorption and high defect tolerance, perovskite materials ranging from nanocrystalline to bulk semiconductors enable efficient TTA-UC in both solution and solid-state systems. After introducing the TTA-UC process and giving a brief overview of its beginnings, we first consider TTA-UC systems based on perovskite nanocrystals and low-dimensional perovskite-inspired materials and the achievements that have been made in those areas. We then focus on the mechanism of bulk perovskite-sensitized TTA-UC, the impact the underlying structure holds, and review the current challenges in perovskite-sensitized solid-state UC and outline future research directions to unlock the full potential of TTA-UC in practical applications.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"125 23","pages":"11426–11460"},"PeriodicalIF":55.8,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145441293","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}