Pub Date : 2026-01-18DOI: 10.1021/acsenergylett.5c04334
Kaiwen Li,Ping He,Haoshen Zhou
Lithium metal batteries (LMBs) represent the most promising candidates for next-generation rechargeable batteries. However, their practical application faces significant challenges from several detrimental transport processes during operation, such as nonuniform Li+ flux, migration of anions under electric fields, and the dissolution and shuttle of cathode active materials to the anode. Metal–organic frameworks (MOFs) have attracted extensive attention for regulating species transport in LMBs due to their high surface area, high porosity, tunable pore structures, and surface polarity. This Review elucidates the ion transport mechanisms in MOFs and examines how structural modifications influence their ion transport behavior. Then the applications of MOF-mediated species transport regulation across various lithium metal battery components are explored in this Review, including lithium metal anode, high-energy cathodes, liquid electrolytes, and solid-state electrolytes. Finally, the advantages and challenges of MOFs for realizing practical and high-performance LMBs are also discussed.
{"title":"Regulating Species Transport in Metal–Organic Frameworks for Lithium Metal Batteries","authors":"Kaiwen Li,Ping He,Haoshen Zhou","doi":"10.1021/acsenergylett.5c04334","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c04334","url":null,"abstract":"Lithium metal batteries (LMBs) represent the most promising candidates for next-generation rechargeable batteries. However, their practical application faces significant challenges from several detrimental transport processes during operation, such as nonuniform Li+ flux, migration of anions under electric fields, and the dissolution and shuttle of cathode active materials to the anode. Metal–organic frameworks (MOFs) have attracted extensive attention for regulating species transport in LMBs due to their high surface area, high porosity, tunable pore structures, and surface polarity. This Review elucidates the ion transport mechanisms in MOFs and examines how structural modifications influence their ion transport behavior. Then the applications of MOF-mediated species transport regulation across various lithium metal battery components are explored in this Review, including lithium metal anode, high-energy cathodes, liquid electrolytes, and solid-state electrolytes. Finally, the advantages and challenges of MOFs for realizing practical and high-performance LMBs are also discussed.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"88 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995086","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-18DOI: 10.1021/acsenergylett.5c04138
Christel I. Koopman,Jelco Albertsma,Monique A. van der Veen,David A. Vermaas
Carbon monoxide in industrial waste gases is often burned and is responsible for about 8% of industrial CO2 emissions. In contrast to CO2 capture, no conventional technologies are available for separating CO from nitrogen at scale. Here, we show that the difference in the CO binding affinity between [NiI(cyclam)]+ and [NiII(cyclam)]2+ can be leveraged in an electrochemical separation method: cycled capture and release of CO through potential control. The carrier, [NiI(cyclam)]+, has a binding constant with CO that was estimated to be 7 × 103 M–1 through the deconvolution of cyclic voltammetry curves. An electroswing between −1.7 V and −1.5 V vs ferrocene is sufficient to switch between the capture and release of CO. A more positive release potential can increase the release rate of CO albeit at the expense of the current efficiency. This work shows that a [Ni(cyclam)]Cl2 carrier can selectively separate and concentrate CO from nitrogen electrochemically.
{"title":"Electrochemically Mediated Separation of Carbon Monoxide Using a Ni-Based Redox Couple","authors":"Christel I. Koopman,Jelco Albertsma,Monique A. van der Veen,David A. Vermaas","doi":"10.1021/acsenergylett.5c04138","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c04138","url":null,"abstract":"Carbon monoxide in industrial waste gases is often burned and is responsible for about 8% of industrial CO2 emissions. In contrast to CO2 capture, no conventional technologies are available for separating CO from nitrogen at scale. Here, we show that the difference in the CO binding affinity between [NiI(cyclam)]+ and [NiII(cyclam)]2+ can be leveraged in an electrochemical separation method: cycled capture and release of CO through potential control. The carrier, [NiI(cyclam)]+, has a binding constant with CO that was estimated to be 7 × 103 M–1 through the deconvolution of cyclic voltammetry curves. An electroswing between −1.7 V and −1.5 V vs ferrocene is sufficient to switch between the capture and release of CO. A more positive release potential can increase the release rate of CO albeit at the expense of the current efficiency. This work shows that a [Ni(cyclam)]Cl2 carrier can selectively separate and concentrate CO from nitrogen electrochemically.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"383 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-18DOI: 10.1021/acsenergylett.5c04138
Christel I. Koopman,Jelco Albertsma,Monique A. van der Veen,David A. Vermaas
Carbon monoxide in industrial waste gases is often burned and is responsible for about 8% of industrial CO2 emissions. In contrast to CO2 capture, no conventional technologies are available for separating CO from nitrogen at scale. Here, we show that the difference in the CO binding affinity between [NiI(cyclam)]+ and [NiII(cyclam)]2+ can be leveraged in an electrochemical separation method: cycled capture and release of CO through potential control. The carrier, [NiI(cyclam)]+, has a binding constant with CO that was estimated to be 7 × 103 M–1 through the deconvolution of cyclic voltammetry curves. An electroswing between −1.7 V and −1.5 V vs ferrocene is sufficient to switch between the capture and release of CO. A more positive release potential can increase the release rate of CO albeit at the expense of the current efficiency. This work shows that a [Ni(cyclam)]Cl2 carrier can selectively separate and concentrate CO from nitrogen electrochemically.
{"title":"Electrochemically Mediated Separation of Carbon Monoxide Using a Ni-Based Redox Couple","authors":"Christel I. Koopman,Jelco Albertsma,Monique A. van der Veen,David A. Vermaas","doi":"10.1021/acsenergylett.5c04138","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c04138","url":null,"abstract":"Carbon monoxide in industrial waste gases is often burned and is responsible for about 8% of industrial CO2 emissions. In contrast to CO2 capture, no conventional technologies are available for separating CO from nitrogen at scale. Here, we show that the difference in the CO binding affinity between [NiI(cyclam)]+ and [NiII(cyclam)]2+ can be leveraged in an electrochemical separation method: cycled capture and release of CO through potential control. The carrier, [NiI(cyclam)]+, has a binding constant with CO that was estimated to be 7 × 103 M–1 through the deconvolution of cyclic voltammetry curves. An electroswing between −1.7 V and −1.5 V vs ferrocene is sufficient to switch between the capture and release of CO. A more positive release potential can increase the release rate of CO albeit at the expense of the current efficiency. This work shows that a [Ni(cyclam)]Cl2 carrier can selectively separate and concentrate CO from nitrogen electrochemically.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"22 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-18DOI: 10.1021/acsenergylett.5c04334
Kaiwen Li,Ping He,Haoshen Zhou
Lithium metal batteries (LMBs) represent the most promising candidates for next-generation rechargeable batteries. However, their practical application faces significant challenges from several detrimental transport processes during operation, such as nonuniform Li+ flux, migration of anions under electric fields, and the dissolution and shuttle of cathode active materials to the anode. Metal–organic frameworks (MOFs) have attracted extensive attention for regulating species transport in LMBs due to their high surface area, high porosity, tunable pore structures, and surface polarity. This Review elucidates the ion transport mechanisms in MOFs and examines how structural modifications influence their ion transport behavior. Then the applications of MOF-mediated species transport regulation across various lithium metal battery components are explored in this Review, including lithium metal anode, high-energy cathodes, liquid electrolytes, and solid-state electrolytes. Finally, the advantages and challenges of MOFs for realizing practical and high-performance LMBs are also discussed.
{"title":"Regulating Species Transport in Metal–Organic Frameworks for Lithium Metal Batteries","authors":"Kaiwen Li,Ping He,Haoshen Zhou","doi":"10.1021/acsenergylett.5c04334","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c04334","url":null,"abstract":"Lithium metal batteries (LMBs) represent the most promising candidates for next-generation rechargeable batteries. However, their practical application faces significant challenges from several detrimental transport processes during operation, such as nonuniform Li+ flux, migration of anions under electric fields, and the dissolution and shuttle of cathode active materials to the anode. Metal–organic frameworks (MOFs) have attracted extensive attention for regulating species transport in LMBs due to their high surface area, high porosity, tunable pore structures, and surface polarity. This Review elucidates the ion transport mechanisms in MOFs and examines how structural modifications influence their ion transport behavior. Then the applications of MOF-mediated species transport regulation across various lithium metal battery components are explored in this Review, including lithium metal anode, high-energy cathodes, liquid electrolytes, and solid-state electrolytes. Finally, the advantages and challenges of MOFs for realizing practical and high-performance LMBs are also discussed.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"4 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-16DOI: 10.1021/acsenergylett.5c04047
Matthew Glasscott, James D. Burgess, Peter Byrley, Maria Fernanda Campa, Mark H. Griep, Alexander P. Kirk, Stephanie A. Mack, Birgit Schwenzer, Ryan M. Welch, Elisabeth Mansfield
Figure 1. Bandgap of various 2D materials. The bandgaps for various 2D materials in the IR–vis–UV range are presented as lines with approximate limits given in eV. Adapted with permission from ref (12). Copyright 2020 Springer Nature. Figure 2. Cathode and anode materials integrating 2D materials. The 2D materials are classified based on their working potentials vs Li/Li+. The atomic structure of these materials are important for introducing different ions and facilitating electronic transport. Adapted with permission from ref (32). Copyright 2020 American Chemical Society. Figure 3. Overview of solid-state hydrogen storage materials based on their volumetric and gravimetric hydrogen density. These materials are plotted with 2020 Department of Energy technology targets. Adapted with permission from ref (39). Copyright 2017 Elsevier. This article references 66 other publications. This article has not yet been cited by other publications.
{"title":"The Strategic Role of 2D Nanomaterials in Grid Modernization","authors":"Matthew Glasscott, James D. Burgess, Peter Byrley, Maria Fernanda Campa, Mark H. Griep, Alexander P. Kirk, Stephanie A. Mack, Birgit Schwenzer, Ryan M. Welch, Elisabeth Mansfield","doi":"10.1021/acsenergylett.5c04047","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c04047","url":null,"abstract":"Figure 1. Bandgap of various 2D materials. The bandgaps for various 2D materials in the IR–vis–UV range are presented as lines with approximate limits given in eV. Adapted with permission from ref (12). Copyright 2020 Springer Nature. Figure 2. Cathode and anode materials integrating 2D materials. The 2D materials are classified based on their working potentials vs Li/Li<sup>+</sup>. The atomic structure of these materials are important for introducing different ions and facilitating electronic transport. Adapted with permission from ref (32). Copyright 2020 American Chemical Society. Figure 3. Overview of solid-state hydrogen storage materials based on their volumetric and gravimetric hydrogen density. These materials are plotted with 2020 Department of Energy technology targets. Adapted with permission from ref (39). Copyright 2017 Elsevier. This article references 66 other publications. This article has not yet been cited by other publications.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"58 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972338","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-16DOI: 10.1021/acsenergylett.5c03345
Li Lei, Bingchen Zhang, Fanghong Zeng, Jun Gan, Huanhuan Wu, Chen Yu, Zhexi Xiao, Lidan Xing, Weishan Li
Phosphorus-based anodes emerge as candidates for sodium-ion batteries (SIBs) but face acute interfacial instability driven by coupled mechanical-chemical degradation, including volume change, polyphosphide dissolution, and pronounced air-induced interfacial oxidation. This Review systematically examines the coupled mechanical-chemical failure mechanisms, covering both mechanical and chemical pathways, and discusses recent advances in interface engineering strategies. Two main approaches involving internal modification and external regulation are detailed to collectively enhance interfacial integrity, suppress irreversible reactions, and improve cycling stability, especially under extreme conditions. Finally, we outline the application potential and future research directions to accelerate the development of phosphorus-based anodes. This Review aims to provide critical guidance for rational interface design to enable practical implementation of phosphorus-based anodes in next-generation SIBs.
{"title":"Unraveling Interfacial Failure Challenges and Mitigation Strategies in Phosphorus-Based Sodium-Ion Batteries","authors":"Li Lei, Bingchen Zhang, Fanghong Zeng, Jun Gan, Huanhuan Wu, Chen Yu, Zhexi Xiao, Lidan Xing, Weishan Li","doi":"10.1021/acsenergylett.5c03345","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c03345","url":null,"abstract":"Phosphorus-based anodes emerge as candidates for sodium-ion batteries (SIBs) but face acute interfacial instability driven by coupled mechanical-chemical degradation, including volume change, polyphosphide dissolution, and pronounced air-induced interfacial oxidation. This Review systematically examines the coupled mechanical-chemical failure mechanisms, covering both mechanical and chemical pathways, and discusses recent advances in interface engineering strategies. Two main approaches involving internal modification and external regulation are detailed to collectively enhance interfacial integrity, suppress irreversible reactions, and improve cycling stability, especially under extreme conditions. Finally, we outline the application potential and future research directions to accelerate the development of phosphorus-based anodes. This Review aims to provide critical guidance for rational interface design to enable practical implementation of phosphorus-based anodes in next-generation SIBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"19 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-16DOI: 10.1021/acsenergylett.5c04187
Karam Yassin, Alexander A. Baranov, Jinliu Zhong, Dario R. Dekel
While the low-temperature (50–80 °C) anion-exchange membrane water electrolysis (AEMWE) field is blooming, the potential for cell operation above 100 °C remains unexplored. Hereafter, we show the first high-temperature AEMWE (HT-AEMWE) cell operating at 110 °C under dry cathode operations with platinum-group metal-free catalysts. Increasing temperature strongly enhances OH– conductivity (119–216 mS/cm at 50–95 °C), water diffusivity (∼6.0-fold at 30–70 °C), and oxygen and hydrogen evolution reaction kinetics (∼30- and ∼6.0-fold increases, at 10–70 °C), altogether translated into substantial cell-level performance gains. The KOHaq-fed HT-AEMWE reaches >5 A/cm2 at <2.2 V and shows negligible degradation (4 μV/h) over a 500 h test at 1.0 A/cm2. Notably, the pure water-fed HT-AEMWE operated for 400 h at 110 °C and 0.5 A/cm2 is extremely stable (6 μV/h), suggesting that the HT-AEMWE technology can eliminate the need for an alkaline liquid electrolyte. This represents a significant landmark for the AEMWE technology.
{"title":"High-Temperature Anion Exchange Membrane Water Electrolysis","authors":"Karam Yassin, Alexander A. Baranov, Jinliu Zhong, Dario R. Dekel","doi":"10.1021/acsenergylett.5c04187","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c04187","url":null,"abstract":"While the low-temperature (50–80 °C) anion-exchange membrane water electrolysis (AEMWE) field is blooming, the potential for cell operation above 100 °C remains unexplored. Hereafter, we show the first high-temperature AEMWE (HT-AEMWE) cell operating at 110 °C under dry cathode operations with platinum-group metal-free catalysts. Increasing temperature strongly enhances OH<sup>–</sup> conductivity (119–216 mS/cm at 50–95 °C), water diffusivity (∼6.0-fold at 30–70 °C), and oxygen and hydrogen evolution reaction kinetics (∼30- and ∼6.0-fold increases, at 10–70 °C), altogether translated into substantial cell-level performance gains. The KOH<sub>aq</sub>-fed HT-AEMWE reaches >5 A/cm<sup>2</sup> at <2.2 V and shows negligible degradation (4 μV/h) over a 500 h test at 1.0 A/cm<sup>2</sup>. Notably, the pure water-fed HT-AEMWE operated for 400 h at 110 °C and 0.5 A/cm<sup>2</sup> is extremely stable (6 μV/h), suggesting that the HT-AEMWE technology can eliminate the need for an alkaline liquid electrolyte. This represents a significant landmark for the AEMWE technology.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"29 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145986665","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-16DOI: 10.1021/acsenergylett.5c04278
Rui Huang, Shaohua Luo, Qi Sun, Lixiong Qian, Shengxue Yan
Fe/Mn-based cathodes are cost-effective for sodium-ion batteries (SIBs) but suffer from slow kinetics and poor air stability. This work detailed Ca/Mg codoped P2/O3–Na0.67Ca0.02Mn0.5Fe0.38Mg0.12O2 (NFM-CM2), elucidating how Ca/Mg codoping balanced the negative capacity impact of inert elements with enhanced anionic redox reversibility (ARR). Thus, Ca/Mg codoping allowed for a delicate trade-off between the negative impact of inert elements on capacity and the positive effect of ARR on extra capacity contribution. This issue has rarely been tackled until recently. Building upon this, NFM-CM2 demonstrated better capacity (202.9 mAh g–1 at 0.1 C), stability (97.5%/85.7%, 100/300 cycles), rate performance (91.9%), and energy density (401.6 Wh kg–1), along with admirable air stability (151.4 mAh g–1, 81.9%). Additionally, there is a more complete picture of textural evolution and charge compensation mechanisms. This research might reshape new perspectives on inactive element doping, inspiring ideas for reversible anionic redox chemistry in designing Fe/Mn-based materials.
铁/锰基阴极对于钠离子电池（sib）来说具有成本效益，但存在动力学缓慢和空气稳定性差的问题。本文详细介绍了Ca/Mg共掺杂P2/ o3 - na0.67 ca0.02 mn0.5 fe0.38 mg0.120 o2 (NFM-CM2)，阐明了Ca/Mg共掺杂如何通过增强阴离子氧化还原可逆性（ARR）来平衡惰性元素的负容量影响。因此，Ca/Mg共掺杂允许在惰性元素对容量的负面影响和ARR对额外容量贡献的积极影响之间进行微妙的权衡。这个问题直到最近才得到解决。在此基础上，NFM-CM2表现出更好的容量（0.1℃时202.9 mAh g-1），稳定性（97.5%/85.7%，100/300次循环），倍率性能（91.9%），能量密度（401.6 Wh kg-1），以及令人钦佩的空气稳定性（151.4 mAh g-1, 81.9%）。此外，对织构演化和电荷补偿机制也有了更全面的了解。该研究可能重塑非活性元素掺杂的新视角，为设计铁/锰基材料的可逆阴离子氧化还原化学提供灵感。
{"title":"New Insights into Inactive-Element Substitution in Fe/Mn Anionic Redox Cathodes","authors":"Rui Huang, Shaohua Luo, Qi Sun, Lixiong Qian, Shengxue Yan","doi":"10.1021/acsenergylett.5c04278","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c04278","url":null,"abstract":"Fe/Mn-based cathodes are cost-effective for sodium-ion batteries (SIBs) but suffer from slow kinetics and poor air stability. This work detailed Ca/Mg codoped P2/O3–Na<sub>0.67</sub>Ca<sub>0.02</sub>Mn<sub>0.5</sub>Fe<sub>0.38</sub>Mg<sub>0.12</sub>O<sub>2</sub> (NFM-CM2), elucidating how Ca/Mg codoping balanced the negative capacity impact of inert elements with enhanced anionic redox reversibility (ARR). Thus, Ca/Mg codoping allowed for a delicate trade-off between the negative impact of inert elements on capacity and the positive effect of ARR on extra capacity contribution. This issue has rarely been tackled until recently. Building upon this, NFM-CM2 demonstrated better capacity (202.9 mAh g<sup>–1</sup> at 0.1 C), stability (97.5%/85.7%, 100/300 cycles), rate performance (91.9%), and energy density (401.6 Wh kg<sup>–1</sup>), along with admirable air stability (151.4 mAh g<sup>–1</sup>, 81.9%). Additionally, there is a more complete picture of textural evolution and charge compensation mechanisms. This research might reshape new perspectives on inactive element doping, inspiring ideas for reversible anionic redox chemistry in designing Fe/Mn-based materials.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"60 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-15DOI: 10.1021/acsenergylett.5c04133
Aodi Wang, Shijie Pan, Guoqing Wang, Xueling Song, Ting Li, Lei Wang
Hydrogen bonding, as a subtle yet powerful noncovalent interaction, plays a critical role in steering proton-coupled electron transfer (PCET) processes; however, its influence within photocatalytic covalent organic frameworks (COFs) has remained underexplored. Here, we present a molecular-level regulation of isoreticular COFs incorporating pyridine- and pyrimidine-based linkers in which the positional arrangement of nitrogen atoms is deliberately modulated to construct distinct hydrogen-bonding microenvironments. As a result, Tp-4,6-Pm exhibits a 7-fold enhancement in H2O2 generation rate compared to Tp-2,6-Pd, achieving a notable solar-to-chemical conversion (SCC) efficiency of 1.48%. Mechanistic studies reveal that hydrogen bonding networks facilitate the generation of surface-bound hydrogen (Had) and stabilize the *OOH intermediate, thereby lowering the energetic barriers for H2O2 photosynthesis. Furthermore, the optimized microenvironment promotes efficient superoxide (•O2–) formation, enabling α-amino C–H annulation with high reactivity. This hydrogen-bonding-regulated microenvironment strategy provides a generalizable approach for activating PCET processes in COFs, offering a powerful design principle for next-generation photocatalytic systems.
{"title":"Hydrogen Bonding Regulated Microenvironments in Covalent Organic Frameworks for Photocatalytic H2O2 Generation and C–H Annulation","authors":"Aodi Wang, Shijie Pan, Guoqing Wang, Xueling Song, Ting Li, Lei Wang","doi":"10.1021/acsenergylett.5c04133","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c04133","url":null,"abstract":"Hydrogen bonding, as a subtle yet powerful noncovalent interaction, plays a critical role in steering proton-coupled electron transfer (PCET) processes; however, its influence within photocatalytic covalent organic frameworks (COFs) has remained underexplored. Here, we present a molecular-level regulation of isoreticular COFs incorporating pyridine- and pyrimidine-based linkers in which the positional arrangement of nitrogen atoms is deliberately modulated to construct distinct hydrogen-bonding microenvironments. As a result, Tp-4,6-Pm exhibits a 7-fold enhancement in H<sub>2</sub>O<sub>2</sub> generation rate compared to Tp-2,6-Pd, achieving a notable solar-to-chemical conversion (SCC) efficiency of 1.48%. Mechanistic studies reveal that hydrogen bonding networks facilitate the generation of surface-bound hydrogen (H<sub>ad</sub>) and stabilize the *OOH intermediate, thereby lowering the energetic barriers for H<sub>2</sub>O<sub>2</sub> photosynthesis. Furthermore, the optimized microenvironment promotes efficient superoxide (<sup>•</sup>O<sub>2</sub><sup>–</sup>) formation, enabling α-amino C–H annulation with high reactivity. This hydrogen-bonding-regulated microenvironment strategy provides a generalizable approach for activating PCET processes in COFs, offering a powerful design principle for next-generation photocatalytic systems.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"180 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968357","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-15DOI: 10.1021/acsenergylett.5c03470
Jinhyuk Choi, Dohyun Kim, Ji-Sang Park, Taiho Park, Yong-Young Noh
Regulating defects at surfaces and grain boundaries arising from uncontrolled crystallization during perovskite film formation and external stresses is crucial for improving the photovoltaic efficiency and long-term stability of perovskite solar cells (PSCs). Phosphine-based Lewis base ligands that can coordinate with Pb2+ have proven to be effective in regulating perovskite crystallization and defect passivation. However, most previous ligand strategies focus on a single point interaction. Herein, we systematically compared the tri(p-tolyl)phosphine and tris(4-methoxyphenyl)phosphine (pMeO) with different functional groups to investigate optimized ligand structure for high-quality perovskite film. Both ligands promote homogeneity and crystallinity through coordination with the Pb–I framework. pMeO exhibits dual-mode interactions by additional hydrogen bonds with organic cations through multidirectionally distributed methoxy substituents in the perovskite, enabling more uniform films with suppressed grain boundary defects and mitigating ion migration. Consequently, pMeO-treated PSCs achieve a power conversion efficiency of 25.46% with enhanced thermal and moisture stability.
{"title":"Synergetic Dual-Mode Interaction of Lewis Base for High Performance Perovskite Solar Cells","authors":"Jinhyuk Choi, Dohyun Kim, Ji-Sang Park, Taiho Park, Yong-Young Noh","doi":"10.1021/acsenergylett.5c03470","DOIUrl":"https://doi.org/10.1021/acsenergylett.5c03470","url":null,"abstract":"Regulating defects at surfaces and grain boundaries arising from uncontrolled crystallization during perovskite film formation and external stresses is crucial for improving the photovoltaic efficiency and long-term stability of perovskite solar cells (PSCs). Phosphine-based Lewis base ligands that can coordinate with Pb<sup>2+</sup> have proven to be effective in regulating perovskite crystallization and defect passivation. However, most previous ligand strategies focus on a single point interaction. Herein, we systematically compared the tri(p-tolyl)phosphine and tris(4-methoxyphenyl)phosphine (pMeO) with different functional groups to investigate optimized ligand structure for high-quality perovskite film. Both ligands promote homogeneity and crystallinity through coordination with the Pb–I framework. pMeO exhibits dual-mode interactions by additional hydrogen bonds with organic cations through multidirectionally distributed methoxy substituents in the perovskite, enabling more uniform films with suppressed grain boundary defects and mitigating ion migration. Consequently, pMeO-treated PSCs achieve a power conversion efficiency of 25.46% with enhanced thermal and moisture stability.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":"1 1","pages":""},"PeriodicalIF":22.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145972472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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