Pub Date : 2024-07-02DOI: 10.1021/acs.chemrev.3c00875
Tsuneo Imamoto
Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality ligands and P-stereogenic phosphorus ligands. Most of the reported ligands belong to the former class. Privileged ones such as BINAP and DuPhos are frequently employed in a wide range of catalytic asymmetric transformations. In contrast, the latter class of P-stereogenic phosphorus ligands has remained a small family for many years mainly because of their synthetic difficulty. The late 1990s saw the emergence of novel P-stereogenic phosphorus ligands with their superior enantioinduction ability in Rh-catalyzed asymmetric hydrogenation reactions. Since then, numerous P-stereogenic phosphorus ligands have been synthesized and used in catalytic asymmetric reactions. This Review summarizes P-stereogenic phosphorus ligands reported thus far, including their stereochemical and electronic properties that afford high to excellent enantioselectivities. Examples of reactions that use this class of ligands are described together with their applications in the construction of key intermediates for the synthesis of optically active natural products and therapeutic agents. The literature covered dates back to 1968 up until December 2023, centering on studies published in the late 1990s and later years.
{"title":"P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis.","authors":"Tsuneo Imamoto","doi":"10.1021/acs.chemrev.3c00875","DOIUrl":"https://doi.org/10.1021/acs.chemrev.3c00875","url":null,"abstract":"<p><p>Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality ligands and P-stereogenic phosphorus ligands. Most of the reported ligands belong to the former class. Privileged ones such as BINAP and DuPhos are frequently employed in a wide range of catalytic asymmetric transformations. In contrast, the latter class of P-stereogenic phosphorus ligands has remained a small family for many years mainly because of their synthetic difficulty. The late 1990s saw the emergence of novel P-stereogenic phosphorus ligands with their superior enantioinduction ability in Rh-catalyzed asymmetric hydrogenation reactions. Since then, numerous P-stereogenic phosphorus ligands have been synthesized and used in catalytic asymmetric reactions. This Review summarizes P-stereogenic phosphorus ligands reported thus far, including their stereochemical and electronic properties that afford high to excellent enantioselectivities. Examples of reactions that use this class of ligands are described together with their applications in the construction of key intermediates for the synthesis of optically active natural products and therapeutic agents. The literature covered dates back to 1968 up until December 2023, centering on studies published in the late 1990s and later years.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":51.4,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489915","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 : 2024-07-02DOI: 10.1021/acs.chemrev.4c00031
Nikolaj G. Koch, Nediljko Budisa
Over 20 years ago, the pyrrolysine encoding translation system was discovered in specific archaea. Our Review provides an overview of how the once obscure pyrrolysyl-tRNA synthetase (PylRS) tRNA pair, originally responsible for accurately translating enzymes crucial in methanogenic metabolic pathways, laid the foundation for the burgeoning field of genetic code expansion. Our primary focus is the discussion of how to successfully engineer the PylRS to recognize new substrates and exhibit higher in vivo activity. We have compiled a comprehensive list of ncAAs incorporable with the PylRS system. Additionally, we also summarize recent successful applications of the PylRS system in creating innovative therapeutic solutions, such as new antibody–drug conjugates, advancements in vaccine modalities, and the potential production of new antimicrobials.
{"title":"Evolution of Pyrrolysyl-tRNA Synthetase: From Methanogenesis to Genetic Code Expansion","authors":"Nikolaj G. Koch, Nediljko Budisa","doi":"10.1021/acs.chemrev.4c00031","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00031","url":null,"abstract":"Over 20 years ago, the pyrrolysine encoding translation system was discovered in specific archaea. Our Review provides an overview of how the once obscure pyrrolysyl-tRNA synthetase (PylRS) tRNA pair, originally responsible for accurately translating enzymes crucial in methanogenic metabolic pathways, laid the foundation for the burgeoning field of genetic code expansion. Our primary focus is the discussion of how to successfully engineer the PylRS to recognize new substrates and exhibit higher <i>in vivo</i> activity. We have compiled a comprehensive list of ncAAs incorporable with the PylRS system. Additionally, we also summarize recent successful applications of the PylRS system in creating innovative therapeutic solutions, such as new antibody–drug conjugates, advancements in vaccine modalities, and the potential production of new antimicrobials.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489787","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 : 2024-06-28DOI: 10.1021/acs.chemrev.4c00007
Vladimir Kubyshkin, Marina Rubini
Within the canonical repertoire of the amino acid involved in protein biogenesis, proline plays a unique role as an amino acid presenting a modified backbone rather than a side-chain. Chemical structures that mimic proline but introduce changes into its specific molecular features are defined as proline analogues. This review article summarizes the existing chemical, physicochemical, and biochemical knowledge about this peculiar family of structures. We group proline analogues from the following compounds: substituted prolines, unsaturated and fused structures, ring size homologues, heterocyclic, e.g., pseudoproline, and bridged proline-resembling structures. We overview (1) the occurrence of proline analogues in nature and their chemical synthesis, (2) physicochemical properties including ring conformation and cis/trans amide isomerization, (3) use in commercial drugs such as nirmatrelvir recently approved against COVID-19, (4) peptide and protein synthesis involving proline analogues, (5) specific opportunities created in peptide engineering, and (6) cases of protein engineering with the analogues. The review aims to provide a summary to anyone interested in using proline analogues in systems ranging from specific biochemical setups to complex biological systems.
{"title":"Proline Analogues.","authors":"Vladimir Kubyshkin, Marina Rubini","doi":"10.1021/acs.chemrev.4c00007","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00007","url":null,"abstract":"<p><p>Within the canonical repertoire of the amino acid involved in protein biogenesis, proline plays a unique role as an amino acid presenting a modified backbone rather than a side-chain. Chemical structures that mimic proline but introduce changes into its specific molecular features are defined as proline analogues. This review article summarizes the existing chemical, physicochemical, and biochemical knowledge about this peculiar family of structures. We group proline analogues from the following compounds: substituted prolines, unsaturated and fused structures, ring size homologues, heterocyclic, e.g., pseudoproline, and bridged proline-resembling structures. We overview (1) the occurrence of proline analogues in nature and their chemical synthesis, (2) physicochemical properties including ring conformation and <i>cis</i>/<i>trans</i> amide isomerization, (3) use in commercial drugs such as nirmatrelvir recently approved against COVID-19, (4) peptide and protein synthesis involving proline analogues, (5) specific opportunities created in peptide engineering, and (6) cases of protein engineering with the analogues. The review aims to provide a summary to anyone interested in using proline analogues in systems ranging from specific biochemical setups to complex biological systems.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":51.4,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464311","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 : 2024-06-27DOI: 10.1021/acs.chemrev.4c00032
Celine V Aarsen, Anna Liguori, Rebecca Mattsson, Mika H Sipponen, Minna Hakkarainen
A powerful toolbox is needed to turn the linear plastic economy into circular. Development of materials designed for mechanical recycling, chemical recycling, and/or biodegradation in targeted end-of-life environment are all necessary puzzle pieces in this process. Polyesters, with reversible ester bonds, are already forerunners in plastic circularity: poly(ethylene terephthalate) (PET) is the most recycled plastic material suitable for mechanical and chemical recycling, while common aliphatic polyesters are biodegradable under favorable conditions, such as industrial compost. However, this circular design needs to be further tailored for different end-of-life options to enable chemical recycling under greener conditions and/or rapid enough biodegradation even under less favorable environmental conditions. Here, we discuss molecular design of the polyester chain targeting enhancement of circularity by incorporation of more easily hydrolyzable ester bonds, additional dynamic bonds, or degradation catalyzing functional groups as part of the polyester chain. The utilization of polyester circularity to design replacement materials for current volume plastics is also reviewed as well as embedment of green catalysts, such as enzymes in biodegradable polyester matrices to facilitate the degradation process.
{"title":"Designed to Degrade: Tailoring Polyesters for Circularity.","authors":"Celine V Aarsen, Anna Liguori, Rebecca Mattsson, Mika H Sipponen, Minna Hakkarainen","doi":"10.1021/acs.chemrev.4c00032","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00032","url":null,"abstract":"<p><p>A powerful toolbox is needed to turn the linear plastic economy into circular. Development of materials designed for mechanical recycling, chemical recycling, and/or biodegradation in targeted end-of-life environment are all necessary puzzle pieces in this process. Polyesters, with reversible ester bonds, are already forerunners in plastic circularity: poly(ethylene terephthalate) (PET) is the most recycled plastic material suitable for mechanical and chemical recycling, while common aliphatic polyesters are biodegradable under favorable conditions, such as industrial compost. However, this circular design needs to be further tailored for different end-of-life options to enable chemical recycling under greener conditions and/or rapid enough biodegradation even under less favorable environmental conditions. Here, we discuss molecular design of the polyester chain targeting enhancement of circularity by incorporation of more easily hydrolyzable ester bonds, additional dynamic bonds, or degradation catalyzing functional groups as part of the polyester chain. The utilization of polyester circularity to design replacement materials for current volume plastics is also reviewed as well as embedment of green catalysts, such as enzymes in biodegradable polyester matrices to facilitate the degradation process.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":51.4,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464310","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 : 2024-06-26DOI: 10.1021/acs.chemrev.4c00291
Zhigang Lei*, Chengna Dai, Jason Hallett and Mark Shiflett,
{"title":"Introduction: Ionic Liquids for Diverse Applications","authors":"Zhigang Lei*, Chengna Dai, Jason Hallett and Mark Shiflett, ","doi":"10.1021/acs.chemrev.4c00291","DOIUrl":"10.1021/acs.chemrev.4c00291","url":null,"abstract":"","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":51.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141448999","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 : 2024-06-26DOI: 10.1021/acs.chemrev.4c00009
Hui Huang, Yi Zheng, Meiqi Chang, Jun Song, Lili Xia, Chenyao Wu, Wencong Jia, Hongze Ren, Wei Feng, Yu Chen
Due to the intrinsic non-invasive nature, cost-effectiveness, high safety, and real-time capabilities, besides diagnostic imaging, ultrasound as a typical mechanical wave has been extensively developed as a physical tool for versatile biomedical applications. Especially, the prosperity of nanotechnology and nanomedicine invigorates the landscape of ultrasound-based medicine. The unprecedented surge in research enthusiasm and dedicated efforts have led to a mass of multifunctional micro-/nanosystems being applied in ultrasound biomedicine, facilitating precise diagnosis, effective treatment, and personalized theranostics. The effective deployment of versatile ultrasound-based micro-/nanosystems in biomedical applications is rooted in a profound understanding of the relationship among composition, structure, property, bioactivity, application, and performance. In this comprehensive review, we elaborate on the general principles regarding the design, synthesis, functionalization, and optimization of ultrasound-based micro-/nanosystems for abundant biomedical applications. In particular, recent advancements in ultrasound-based micro-/nanosystems for diagnostic imaging are meticulously summarized. Furthermore, we systematically elucidate state-of-the-art studies concerning recent progress in ultrasound-based micro-/nanosystems for therapeutic applications targeting various pathological abnormalities including cancer, bacterial infection, brain diseases, cardiovascular diseases, and metabolic diseases. Finally, we conclude and provide an outlook on this research field with an in-depth discussion of the challenges faced and future developments for further extensive clinical translation and application.
{"title":"Ultrasound-Based Micro-/Nanosystems for Biomedical Applications.","authors":"Hui Huang, Yi Zheng, Meiqi Chang, Jun Song, Lili Xia, Chenyao Wu, Wencong Jia, Hongze Ren, Wei Feng, Yu Chen","doi":"10.1021/acs.chemrev.4c00009","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00009","url":null,"abstract":"<p><p>Due to the intrinsic non-invasive nature, cost-effectiveness, high safety, and real-time capabilities, besides diagnostic imaging, ultrasound as a typical mechanical wave has been extensively developed as a physical tool for versatile biomedical applications. Especially, the prosperity of nanotechnology and nanomedicine invigorates the landscape of ultrasound-based medicine. The unprecedented surge in research enthusiasm and dedicated efforts have led to a mass of multifunctional micro-/nanosystems being applied in ultrasound biomedicine, facilitating precise diagnosis, effective treatment, and personalized theranostics. The effective deployment of versatile ultrasound-based micro-/nanosystems in biomedical applications is rooted in a profound understanding of the relationship among composition, structure, property, bioactivity, application, and performance. In this comprehensive review, we elaborate on the general principles regarding the design, synthesis, functionalization, and optimization of ultrasound-based micro-/nanosystems for abundant biomedical applications. In particular, recent advancements in ultrasound-based micro-/nanosystems for diagnostic imaging are meticulously summarized. Furthermore, we systematically elucidate state-of-the-art studies concerning recent progress in ultrasound-based micro-/nanosystems for therapeutic applications targeting various pathological abnormalities including cancer, bacterial infection, brain diseases, cardiovascular diseases, and metabolic diseases. Finally, we conclude and provide an outlook on this research field with an in-depth discussion of the challenges faced and future developments for further extensive clinical translation and application.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":51.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453623","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 : 2024-06-24DOI: 10.1021/acs.chemrev.4c00066
Li Cao, Lei Wang
Interactions among biomacromolecules, predominantly noncovalent, underpin biological processes. However, recent advancements in biospecific chemistry have enabled the creation of specific covalent bonds between biomolecules, both in vitro and in vivo. This Review traces the evolution of biospecific chemistry in proteins, emphasizing the role of genetically encoded latent bioreactive amino acids. These amino acids react selectively with adjacent natural groups through proximity-enabled bioreactivity, enabling targeted covalent linkages. We explore various latent bioreactive amino acids designed to target different protein residues, ribonucleic acids, and carbohydrates. We then discuss how these novel covalent linkages can drive challenging protein properties and capture transient protein-protein and protein-RNA interactions in vivo. Additionally, we examine the application of covalent peptides as potential therapeutic agents and site-specific conjugates for native antibodies, highlighting their capacity to form stable linkages with target molecules. A significant focus is placed on proximity-enabled reactive therapeutics (PERx), a pioneering technology in covalent protein therapeutics. We detail its wide-ranging applications in immunotherapy, viral neutralization, and targeted radionuclide therapy. Finally, we present a perspective on the existing challenges within biospecific chemistry and discuss the potential avenues for future exploration and advancement in this rapidly evolving field.
{"title":"Biospecific Chemistry for Covalent Linking of Biomacromolecules.","authors":"Li Cao, Lei Wang","doi":"10.1021/acs.chemrev.4c00066","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00066","url":null,"abstract":"<p><p>Interactions among biomacromolecules, predominantly noncovalent, underpin biological processes. However, recent advancements in biospecific chemistry have enabled the creation of specific covalent bonds between biomolecules, both in vitro and in vivo. This Review traces the evolution of biospecific chemistry in proteins, emphasizing the role of genetically encoded latent bioreactive amino acids. These amino acids react selectively with adjacent natural groups through proximity-enabled bioreactivity, enabling targeted covalent linkages. We explore various latent bioreactive amino acids designed to target different protein residues, ribonucleic acids, and carbohydrates. We then discuss how these novel covalent linkages can drive challenging protein properties and capture transient protein-protein and protein-RNA interactions in vivo. Additionally, we examine the application of covalent peptides as potential therapeutic agents and site-specific conjugates for native antibodies, highlighting their capacity to form stable linkages with target molecules. A significant focus is placed on proximity-enabled reactive therapeutics (PERx), a pioneering technology in covalent protein therapeutics. We detail its wide-ranging applications in immunotherapy, viral neutralization, and targeted radionuclide therapy. Finally, we present a perspective on the existing challenges within biospecific chemistry and discuss the potential avenues for future exploration and advancement in this rapidly evolving field.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":51.4,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141445548","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 : 2024-06-20DOI: 10.1021/acs.chemrev.3c00831
Jun Liang, Kemeng Xiao, Xinyu Wang, Tianfeng Hou, Cuiping Zeng, Xiang Gao, Bo Wang, Chao Zhong
Nanomaterial-microorganism hybrid systems (NMHSs), integrating semiconductor nanomaterials with microorganisms, present a promising platform for broadband solar energy harvesting, high-efficiency carbon reduction, and sustainable chemical production. While studies underscore its potential in diverse solar-to-chemical energy conversions, prevailing NMHSs grapple with suboptimal energy conversion efficiency. Such limitations stem predominantly from an insufficient systematic exploration of the mechanisms dictating solar energy flow. This review provides a systematic overview of the notable advancements in this nascent field, with a particular focus on the discussion of three pivotal steps of energy flow: solar energy capture, cross-membrane energy transport, and energy conversion into chemicals. While key challenges faced in each stage are independently identified and discussed, viable solutions are correspondingly postulated. In view of the interplay of the three steps in affecting the overall efficiency of solar-to-chemical energy conversion, subsequent discussions thus take an integrative and systematic viewpoint to comprehend, analyze and improve the solar energy flow in the current NMHSs of different configurations, and highlighting the contemporary techniques that can be employed to investigate various aspects of energy flow within NMHSs. Finally, a concluding section summarizes opportunities for future research, providing a roadmap for the continued development and optimization of NMHSs.
{"title":"Revisiting Solar Energy Flow in Nanomaterial-Microorganism Hybrid Systems.","authors":"Jun Liang, Kemeng Xiao, Xinyu Wang, Tianfeng Hou, Cuiping Zeng, Xiang Gao, Bo Wang, Chao Zhong","doi":"10.1021/acs.chemrev.3c00831","DOIUrl":"https://doi.org/10.1021/acs.chemrev.3c00831","url":null,"abstract":"<p><p>Nanomaterial-microorganism hybrid systems (NMHSs), integrating semiconductor nanomaterials with microorganisms, present a promising platform for broadband solar energy harvesting, high-efficiency carbon reduction, and sustainable chemical production. While studies underscore its potential in diverse solar-to-chemical energy conversions, prevailing NMHSs grapple with suboptimal energy conversion efficiency. Such limitations stem predominantly from an insufficient systematic exploration of the mechanisms dictating solar energy flow. This review provides a systematic overview of the notable advancements in this nascent field, with a particular focus on the discussion of three pivotal steps of energy flow: solar energy capture, cross-membrane energy transport, and energy conversion into chemicals. While key challenges faced in each stage are independently identified and discussed, viable solutions are correspondingly postulated. In view of the interplay of the three steps in affecting the overall efficiency of solar-to-chemical energy conversion, subsequent discussions thus take an integrative and systematic viewpoint to comprehend, analyze and improve the solar energy flow in the current NMHSs of different configurations, and highlighting the contemporary techniques that can be employed to investigate various aspects of energy flow within NMHSs. Finally, a concluding section summarizes opportunities for future research, providing a roadmap for the continued development and optimization of NMHSs.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141425669","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 : 2024-06-17DOI: 10.1021/acs.chemrev.4c00008
Inyoung Jang, Juliana S A Carneiro, Joshua O Crawford, Yoon Jin Cho, Sahanaz Parvin, Diego A Gonzalez-Casamachin, Jonas Baltrusaitis, Ryan P Lively, Eranda Nikolla
Interest in energy-to-X and X-to-energy (where X represents green hydrogen, carbon-based fuels, or ammonia) technologies has expanded the field of electrochemical conversion and storage. Solid oxide electrochemical cells (SOCs) are among the most promising technologies for these processes. Their unmatched conversion efficiencies result from favorable thermodynamics and kinetics at elevated operating temperatures (400-900 °C). These solid-state electrochemical systems exhibit flexibility in reversible operation between fuel cell and electrolysis modes and can efficiently utilize a variety of fuels. However, electrocatalytic materials at SOC electrodes remain nonoptimal for facilitating reversible operation and fuel flexibility. In this Review, we explore the diverse range of electrocatalytic materials utilized in oxygen-ion-conducting SOCs (O-SOCs) and proton-conducting SOCs (H-SOCs). We examine their electrochemical activity as a function of composition and structure across different electrochemical reactions to highlight characteristics that lead to optimal catalytic performance. Catalyst deactivation mechanisms under different operating conditions are discussed to assess the bottlenecks in performance. We conclude by providing guidelines for evaluating the electrochemical performance of electrode catalysts in SOCs and for designing effective catalysts to achieve flexibility in fuel usage and mode of operation.
人们对 "能量转化为 X "和 "X 转化为能量"(其中 X 代表绿色氢气、碳基燃料或氨)技术的兴趣扩大了电化学转换和储存领域。固体氧化物电化学电池(SOC)是这些工艺中最有前途的技术之一。在工作温度较高(400-900 °C)的条件下,其热力学和动力学性能良好,因而具有无与伦比的转换效率。这些固态电化学系统可在燃料电池和电解模式之间灵活地进行可逆操作,并能有效地利用各种燃料。然而,SOC 电极的电催化材料在促进可逆操作和燃料灵活性方面仍不理想。在本综述中,我们探讨了氧离子传导 SOC(O-SOC)和质子传导 SOC(H-SOC)中使用的各种电催化材料。我们研究了它们在不同电化学反应中作为组成和结构函数的电化学活性,以突出可实现最佳催化性能的特点。我们还讨论了不同操作条件下的催化剂失活机制,以评估性能瓶颈。最后,我们为评估 SOC 中电极催化剂的电化学性能以及设计有效的催化剂以实现燃料使用和操作模式的灵活性提供了指导。
{"title":"Electrocatalysis in Solid Oxide Fuel Cells and Electrolyzers.","authors":"Inyoung Jang, Juliana S A Carneiro, Joshua O Crawford, Yoon Jin Cho, Sahanaz Parvin, Diego A Gonzalez-Casamachin, Jonas Baltrusaitis, Ryan P Lively, Eranda Nikolla","doi":"10.1021/acs.chemrev.4c00008","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00008","url":null,"abstract":"<p><p>Interest in energy-to-X and X-to-energy (where X represents green hydrogen, carbon-based fuels, or ammonia) technologies has expanded the field of electrochemical conversion and storage. Solid oxide electrochemical cells (SOCs) are among the most promising technologies for these processes. Their unmatched conversion efficiencies result from favorable thermodynamics and kinetics at elevated operating temperatures (400-900 °C). These solid-state electrochemical systems exhibit flexibility in reversible operation between fuel cell and electrolysis modes and can efficiently utilize a variety of fuels. However, electrocatalytic materials at SOC electrodes remain nonoptimal for facilitating reversible operation and fuel flexibility. In this Review, we explore the diverse range of electrocatalytic materials utilized in oxygen-ion-conducting SOCs (O-SOCs) and proton-conducting SOCs (H-SOCs). We examine their electrochemical activity as a function of composition and structure across different electrochemical reactions to highlight characteristics that lead to optimal catalytic performance. Catalyst deactivation mechanisms under different operating conditions are discussed to assess the bottlenecks in performance. We conclude by providing guidelines for evaluating the electrochemical performance of electrode catalysts in SOCs and for designing effective catalysts to achieve flexibility in fuel usage and mode of operation.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141416585","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}