Wenqi Li, Yingdong Chen, Tao Chen, Jing Zhao, Qianjin Zhang, Wei Chen, Mingchang Zhang, Haitao Gu, Jiajun Fu
Silicon microparticle (SiMP) anodes are promising candidates for lithium-ion and post lithium-ion batteries owing to its less interfacial reactions and higher tap density than nanostructured silicon anodes. However, the intractable volume expansion/contraction of micro-sized silicon upon cycling results in severe particle pulverization/disintegration and unstable solid-electrolyte interphase. Binders play an essential role in dissipating huge mechanical stress and promoting the lithium-ion diffusion kinetics of silicon anodes. Herein, we design a mechanoresponsive dual cross-linking elastomeric network that incorporates a supramolecular zwitterionic reorganizable network into the hydrogen-bonded polyacrylic acid network to stabilize the interphase and improve cycling stability of silicon microparticle anodes. Such dual-network design enables effective stress dissipation and spontaneous crack repair via sequential dissociation of weak supramolecular zwitterionic interaction and strong dimeric H-bonds of zwitterions upon repeated lithiation/delithiation. Benefiting from these merits, the resultant SiMP anodes using the mechanoresponsive elastomeric binder exhibits a high reversible capacity of 1625.1 mAh g−1 at 2.0 A g−1 after 400 cycles. The assembled full cells with LiNi0.8Mn0.1Co0.1O2 cathodes afford a reversible capacity of 105.2 mAh g−1 after 100 cycles. This work demonstrates the great potential of mechanoresponsive elastomeric binder in developing state-of-the-art high-performance silicon microparticle anodes toward high-energy-density lithium-battery applications.
{"title":"Mechanoresponsive Elastomeric Binder Toughened by Supramolecular Zwitterionic Network for Silicon Microparticle Anodes†","authors":"Wenqi Li, Yingdong Chen, Tao Chen, Jing Zhao, Qianjin Zhang, Wei Chen, Mingchang Zhang, Haitao Gu, Jiajun Fu","doi":"10.1039/d4ta08921a","DOIUrl":"https://doi.org/10.1039/d4ta08921a","url":null,"abstract":"Silicon microparticle (SiMP) anodes are promising candidates for lithium-ion and post lithium-ion batteries owing to its less interfacial reactions and higher tap density than nanostructured silicon anodes. However, the intractable volume expansion/contraction of micro-sized silicon upon cycling results in severe particle pulverization/disintegration and unstable solid-electrolyte interphase. Binders play an essential role in dissipating huge mechanical stress and promoting the lithium-ion diffusion kinetics of silicon anodes. Herein, we design a mechanoresponsive dual cross-linking elastomeric network that incorporates a supramolecular zwitterionic reorganizable network into the hydrogen-bonded polyacrylic acid network to stabilize the interphase and improve cycling stability of silicon microparticle anodes. Such dual-network design enables effective stress dissipation and spontaneous crack repair via sequential dissociation of weak supramolecular zwitterionic interaction and strong dimeric H-bonds of zwitterions upon repeated lithiation/delithiation. Benefiting from these merits, the resultant SiMP anodes using the mechanoresponsive elastomeric binder exhibits a high reversible capacity of 1625.1 mAh g−1 at 2.0 A g−1 after 400 cycles. The assembled full cells with LiNi0.8Mn0.1Co0.1O2 cathodes afford a reversible capacity of 105.2 mAh g−1 after 100 cycles. This work demonstrates the great potential of mechanoresponsive elastomeric binder in developing state-of-the-art high-performance silicon microparticle anodes toward high-energy-density lithium-battery applications.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"6 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Guirong Yu, Na Li, Xiao Li, Yuhao Guo, Tingjiang Yan
Aluminum oxides (Al2O3, AlOOH) have been extensively studied as adsorbents, porous materials, and catalyst supports. However, they rarely exhibit photocatalytic applications due to the lack of active centers and light absorption properties. In this work, we present a novel approach in which highly dispersed copper (Cu) nanoparticles are loaded onto defect-laden AlO(OH)x nanocrystals, serving as an effective photocatalyst for the reverse water gas shift (RWGS) reaction with a remarkable near-unity (∼99%) selectivity. The surface frustrated Lewis pair (SFLP) on AlO(OH)x provides catalytic sites to activate H2 and CO2 molecules. Meanwhile, the localized surface plasmon resonance (LSPR) of Cu nanoparticles can generate sufficient hot electrons to facilitate H2 dissociation and thereby the reduction of CO2. The synergetic effect of SFLP and LSPR tunes the catalyst from inert to highly reactive by tailoring the surface structure and electronic property, providing a new perspective for the potential application of traditional industrial catalysts and/or supports.
{"title":"Synergetic effect of surface frustrated Lewis pair and localized surface plasmon resonance on tuning catalyst from inert to highly reactive for photocatalytic CO2 hydrogenation","authors":"Guirong Yu, Na Li, Xiao Li, Yuhao Guo, Tingjiang Yan","doi":"10.1039/d5ta01792k","DOIUrl":"https://doi.org/10.1039/d5ta01792k","url":null,"abstract":"Aluminum oxides (Al2O3, AlOOH) have been extensively studied as adsorbents, porous materials, and catalyst supports. However, they rarely exhibit photocatalytic applications due to the lack of active centers and light absorption properties. In this work, we present a novel approach in which highly dispersed copper (Cu) nanoparticles are loaded onto defect-laden AlO(OH)x nanocrystals, serving as an effective photocatalyst for the reverse water gas shift (RWGS) reaction with a remarkable near-unity (∼99%) selectivity. The surface frustrated Lewis pair (SFLP) on AlO(OH)x provides catalytic sites to activate H2 and CO2 molecules. Meanwhile, the localized surface plasmon resonance (LSPR) of Cu nanoparticles can generate sufficient hot electrons to facilitate H2 dissociation and thereby the reduction of CO2. The synergetic effect of SFLP and LSPR tunes the catalyst from inert to highly reactive by tailoring the surface structure and electronic property, providing a new perspective for the potential application of traditional industrial catalysts and/or supports.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"37 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766886","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Amit Nagar, Akhtar Alam, Pradip Pachfule, C. M. Nagaraja
Covalent organic frameworks (COFs) can be precisely designed through the choice of organic building blocks, bridging linkages and topologies with tailored photophysical properties, which consequently leads to their significantly different photocatalytic performances. Besides, the orientation of the bridge linkages in the COF backbone plays a critical role in facilitating photogenerated charge separation and migration, which is one of the most important factors for photocatalysis. Herein, we demonstrate a pair of constitutionally cyano-vinylene-linked isomeric COFs (Py-PaCN and PyCN-Pa) with the same composition but different atomic arrangements of cyano-vinylene linkages to unveil their insightful structure-activity relationship for photocatalytic hydrogen generation via water splitting. The hydrogen evolution rate of Py-PaCN COF reaches up to 12.1 mmol g-1 h-1 (AQY = 7.15 %), which is about three times higher than that of its isomer PyCN-Pa COF with 4.3 mmol g-1 h-1 (AQY = 2.54 %), using ascorbic acid as a sacrificial agent. These minor structural changes in COFs result in remarkable variations in their light-harvesting, optoelectronic, and redox properties, resulting in divergent photocatalytic hydrogen evolution activity. This investigation of the constitutional isomerism of linkages in COFs will help in the selection of the right building blocks with distinct functionality in the design and precise tuning of the photophysical properties of COFs.
{"title":"Isomeric Cyano-vinylene-linked Covalent Organic Frameworks and their Impact on Photocatalytic Hydrogen Evolution","authors":"Amit Nagar, Akhtar Alam, Pradip Pachfule, C. M. Nagaraja","doi":"10.1039/d5ta01539a","DOIUrl":"https://doi.org/10.1039/d5ta01539a","url":null,"abstract":"Covalent organic frameworks (COFs) can be precisely designed through the choice of organic building blocks, bridging linkages and topologies with tailored photophysical properties, which consequently leads to their significantly different photocatalytic performances. Besides, the orientation of the bridge linkages in the COF backbone plays a critical role in facilitating photogenerated charge separation and migration, which is one of the most important factors for photocatalysis. Herein, we demonstrate a pair of constitutionally cyano-vinylene-linked isomeric COFs (Py-PaCN and PyCN-Pa) with the same composition but different atomic arrangements of cyano-vinylene linkages to unveil their insightful structure-activity relationship for photocatalytic hydrogen generation via water splitting. The hydrogen evolution rate of Py-PaCN COF reaches up to 12.1 mmol g-1 h-1 (AQY = 7.15 %), which is about three times higher than that of its isomer PyCN-Pa COF with 4.3 mmol g-1 h-1 (AQY = 2.54 %), using ascorbic acid as a sacrificial agent. These minor structural changes in COFs result in remarkable variations in their light-harvesting, optoelectronic, and redox properties, resulting in divergent photocatalytic hydrogen evolution activity. This investigation of the constitutional isomerism of linkages in COFs will help in the selection of the right building blocks with distinct functionality in the design and precise tuning of the photophysical properties of COFs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"41 2 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766896","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Reversible protonic ceramic electrochemical cells (R-PCECs) have demonstrated great potential for efficient energy conversion and storage, expected to break through the limitations in traditional cell systems. However, the performance of R-PCECs is often constrained by the air electrode, where oxygen reduction/evolution reactions occur. Herein, we report a composite electrode of spinel oxide MnCo1.9Cu0.1O4 (MCCO) and BaZr0.8Y0.2O3 (BZY), at an optimized ratio of MCCO to BZY = 9:1, showing a low area-specific resistance of 0.107 Ω cm2 at 700 oC. Cells with this composite air electrode exhibit the highest performance among cells with spinel electrodes: a maximum power density (Pmax) of 1.81 W cm-2 in fuel cells mode, and a current density at 1.3 V of -3.57 A cm-2 using electrolysis mode at 700 oC. Moreover, the cells demonstrate remarkable stability in reversible operation for 70 hours and 15 cycles during ORR-OER cycling testing, at ±0.5 A cm-2. The enhanced activity and durability are likely attributed to the facilitated oxygen/proton transport and the increased concentration of oxygen vacancies after Cu doping, as indicated by the analyses of X-ray photoelectron spectroscopy, and distribution of relaxation time.
{"title":"Achieving active and durable oxygen reduction/evolution reactions on protonic ceramic electrochemical cells with spinel-based air electrodes","authors":"Wanqing Deng, Yangsen Xu, Xirui Zhang, Jiaojiao Xia, Kang Xu, Hui Gao, Bote Zhao, Yu Chen","doi":"10.1039/d4ta08703h","DOIUrl":"https://doi.org/10.1039/d4ta08703h","url":null,"abstract":"Reversible protonic ceramic electrochemical cells (R-PCECs) have demonstrated great potential for efficient energy conversion and storage, expected to break through the limitations in traditional cell systems. However, the performance of R-PCECs is often constrained by the air electrode, where oxygen reduction/evolution reactions occur. Herein, we report a composite electrode of spinel oxide MnCo1.9Cu0.1O4 (MCCO) and BaZr0.8Y0.2O3 (BZY), at an optimized ratio of MCCO to BZY = 9:1, showing a low area-specific resistance of 0.107 Ω cm2 at 700 oC. Cells with this composite air electrode exhibit the highest performance among cells with spinel electrodes: a maximum power density (Pmax) of 1.81 W cm-2 in fuel cells mode, and a current density at 1.3 V of -3.57 A cm-2 using electrolysis mode at 700 oC. Moreover, the cells demonstrate remarkable stability in reversible operation for 70 hours and 15 cycles during ORR-OER cycling testing, at ±0.5 A cm-2. The enhanced activity and durability are likely attributed to the facilitated oxygen/proton transport and the increased concentration of oxygen vacancies after Cu doping, as indicated by the analyses of X-ray photoelectron spectroscopy, and distribution of relaxation time.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"34 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rui Jin, Shihao Li, Wei Zhou, Yi Zhang, Ziyue Qiu, Yuhang Zhang, Huiru Wang, Jie Li, Yanqing Lai, Zhian Zhang
Elemental doping is an effective strategy to enhance the structural stability of O3-type layered cathodes, but few studies focus on the influence difference of dopants on sodium-ion diffusion kinetics during material synthesis and charge-discharge processes. Herein, two Ca-incorporated materials, pre-doped and post-doped Na1-2xCaxNi0.5Mn0.5O2 accompanied by Na vacancies were successfully synthesized. Ca2+ pre-doping inhibits Na+ diffusion into the bulk during synthesis and consequently causes electrochemical performance degradation, while the post-doping strategy by introducing Ca2+ after the synthesis of NNM, effectively circumvents these detrimental effects. The designed post-doping sample enlarges Na interlayer spacing with fast Na+ diffusion behavior and reinforces layered structure with “pillar” effect strong Ca2+-O2- bond, thus enhancing rate capability and cyclic stability. Meanwhile, enhanced Na+ diffusion kinetics ensures uniform phase transitions from the surface to the bulk. Consequently, the post-doping approach provides an inspiration for the design and synthesis of high-performance O3-type Na-layered oxides.
{"title":"Na layer pillar ions post-doping facilitating diffusion kinetics and structural stability in NaNi0.5Mn0.5O2","authors":"Rui Jin, Shihao Li, Wei Zhou, Yi Zhang, Ziyue Qiu, Yuhang Zhang, Huiru Wang, Jie Li, Yanqing Lai, Zhian Zhang","doi":"10.1039/d5ta00764j","DOIUrl":"https://doi.org/10.1039/d5ta00764j","url":null,"abstract":"Elemental doping is an effective strategy to enhance the structural stability of O3-type layered cathodes, but few studies focus on the influence difference of dopants on sodium-ion diffusion kinetics during material synthesis and charge-discharge processes. Herein, two Ca-incorporated materials, pre-doped and post-doped Na1-2xCaxNi0.5Mn0.5O2 accompanied by Na vacancies were successfully synthesized. Ca2+ pre-doping inhibits Na+ diffusion into the bulk during synthesis and consequently causes electrochemical performance degradation, while the post-doping strategy by introducing Ca2+ after the synthesis of NNM, effectively circumvents these detrimental effects. The designed post-doping sample enlarges Na interlayer spacing with fast Na+ diffusion behavior and reinforces layered structure with “pillar” effect strong Ca2+-O2- bond, thus enhancing rate capability and cyclic stability. Meanwhile, enhanced Na+ diffusion kinetics ensures uniform phase transitions from the surface to the bulk. Consequently, the post-doping approach provides an inspiration for the design and synthesis of high-performance O3-type Na-layered oxides.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"37 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two-dimensional transition metal dichalcogenides (2DTMDCs) are promising in quantum computing, flexible electronics, spintronics, sustainable energy systems, and advanced healthcare. To transition 2DTMDCs from lab to industry, it is crucial to develop scalable and industrially compatible strategies for precisely modulating novel quantum states. In this review, we provide a new classification of atomic-level manufacturing strategies for quantum state manipulation of 2DTMDCs beyond conventional exfoliation and restacking. We begin by summarizing emerging synthesis strategies for high-quality intrinsic 2DTMDCs and approaches for atomic-level engineering. We then explore the novel quantum phenomena that arise from these modifications, examining their underlying mechanisms in three key aspects: (a) quantum state manipulation in intrinsic 2DTMDCs, (b) quantum state engineering through intrinsic atomic engineering, and (c) quantum state modulation via extrinsic heteroatom incorporation. Finally, we discuss the challenges and future prospects of atomic-scale manufacturing in 2DTMDCs, providing insights into potential research directions.
{"title":"Recent Progress in Atomic-level Manufacturing of Two-Dimensional Transition Metal Dichalcogenides beyond exfoliation and restacking","authors":"Huihui Lin, Yang Meng","doi":"10.1039/d5ta01124h","DOIUrl":"https://doi.org/10.1039/d5ta01124h","url":null,"abstract":"Two-dimensional transition metal dichalcogenides (2DTMDCs) are promising in quantum computing, flexible electronics, spintronics, sustainable energy systems, and advanced healthcare. To transition 2DTMDCs from lab to industry, it is crucial to develop scalable and industrially compatible strategies for precisely modulating novel quantum states. In this review, we provide a new classification of atomic-level manufacturing strategies for quantum state manipulation of 2DTMDCs beyond conventional exfoliation and restacking. We begin by summarizing emerging synthesis strategies for high-quality intrinsic 2DTMDCs and approaches for atomic-level engineering. We then explore the novel quantum phenomena that arise from these modifications, examining their underlying mechanisms in three key aspects: (a) quantum state manipulation in intrinsic 2DTMDCs, (b) quantum state engineering through intrinsic atomic engineering, and (c) quantum state modulation via extrinsic heteroatom incorporation. Finally, we discuss the challenges and future prospects of atomic-scale manufacturing in 2DTMDCs, providing insights into potential research directions.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"38 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766894","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Conjugated porous polymers (CPPs) with a donor–acceptor (D–A) molecular structure usually exhibit good photocatalytic hydrogen evolution (PHE). The rational design of an electron donor and an electron acceptor is the key point to realize high photocatalytic performance. In this work, using dibenzothiophene sulfone (DBTO) as an electron acceptor and N-methyl-phenothiazine (MPTZ) as an electron donor, a donor–acceptor (D–A) structured conjugated porous polymer (PTBT) was prepared. To further enhance the conjugation of the polymer, N-phenyl-phenothiazine (PPTZ) was substituted for MPTZ, giving the photocatalyst PPTBT high mobility of light-generated carriers. Without Pt photosensitizers, PPTBT showed remarkable efficiency in hydrogen evolution, reaching 63.96 mmol g−1 h−1 under visible light illumination (λ ≥ 420 nm), with a quantum yield of 2.2% at 475 nm. To further investigate the influence of the intramolecular electric field and surface properties on the photocatalytic hydrogen production (PHP) properties, by oxidizing the phenothiazine units, PTOBT and PPTOBT were synthesized. The results indicate that although the electron donor combined with a sulfone structure increases the specific surface area of the polymer, it does not improve the photocatalytic hydrogen evolution performance, which could be attributed to the competitive influence of the intramolecular electric field and surface hydrophilicity. Finally, for a deeper understanding, the redox mechanism study of the photocatalysts, EPR analysis and DFT calculations were performed to study the free radicals and detailed electronic properties of both ground and excited states in the photocatalytic system, respectively.
{"title":"The competitive influence of the intramolecular electric field and hydrophilic active sites of D–A conjugated porous polymers on photocatalytic hydrogen evolution performance","authors":"Yongzhen Yang, Fei Zhao, Xinyi Feng, Jinsheng Zhao, Zhen Xu","doi":"10.1039/d5ta00518c","DOIUrl":"https://doi.org/10.1039/d5ta00518c","url":null,"abstract":"Conjugated porous polymers (CPPs) with a donor–acceptor (D–A) molecular structure usually exhibit good photocatalytic hydrogen evolution (PHE). The rational design of an electron donor and an electron acceptor is the key point to realize high photocatalytic performance. In this work, using dibenzothiophene sulfone (DBTO) as an electron acceptor and <em>N</em>-methyl-phenothiazine (MPTZ) as an electron donor, a donor–acceptor (D–A) structured conjugated porous polymer (PTBT) was prepared. To further enhance the conjugation of the polymer, <em>N</em>-phenyl-phenothiazine (PPTZ) was substituted for MPTZ, giving the photocatalyst PPTBT high mobility of light-generated carriers. Without Pt photosensitizers, PPTBT showed remarkable efficiency in hydrogen evolution, reaching 63.96 mmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small> under visible light illumination (<em>λ</em> ≥ 420 nm), with a quantum yield of 2.2% at 475 nm. To further investigate the influence of the intramolecular electric field and surface properties on the photocatalytic hydrogen production (PHP) properties, by oxidizing the phenothiazine units, PTOBT and PPTOBT were synthesized. The results indicate that although the electron donor combined with a sulfone structure increases the specific surface area of the polymer, it does not improve the photocatalytic hydrogen evolution performance, which could be attributed to the competitive influence of the intramolecular electric field and surface hydrophilicity. Finally, for a deeper understanding, the redox mechanism study of the photocatalysts, EPR analysis and DFT calculations were performed to study the free radicals and detailed electronic properties of both ground and excited states in the photocatalytic system, respectively.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"58 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766885","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Timothy Harte, Bhagya Dharmasiri, Žan Simon, David J. Hayne, Daniel J. Eyckens, Luke C. Henderson
Solvate ionic liquids (SILs) represent an expanding subclass of ionic liquids (ILs), formed through the chelation of the cationic species, typically by an oligoether, and an array of charge diffuse anions. Since their first report, SILs have garnered significant attention for their characteristic ionic liquid physicochemical properties, including high thermal stability, negligible vapour pressure, and tailored solvation dynamics, while being simple to synthesise and cost effective. These factors position SILs as promising candidates for next-generation energy storage applications, including lithium-ion (Li-ion), lithium–sulfur (Li–S), lithium–air (Li–air), lithium-redox, all-solid-state lithium batteries (ASLBs), as well as electric double layer transistors (EDLTs), thermoelectrochemical systems, piezoelectric generators and capacitor/supercapacitor devices. This review traces the evolution of SILs, from foundational studies on their structural and dynamic properties to contemporary advancements in their synthesis and application. SILs modular design potential, through ligand, cation, and anion modifications is evaluated. The multifaceted roles of SILs across various systems are explored, including their applications in electrodeposition and metal extraction, their function as reaction media in organic synthesis, their use as pharmaceutical delivery agents, and their role as constituents and curing catalysts in polymer composites. Furthermore, critical challenges such as optimising ion transport, understanding coordination dynamics, and mitigating environmental impacts are outlined. By integrating experimental insights with computational modeling, this review provides a comprehensive framework to guide future investigations, paving the way for the sustainable development of SILs across scientific and technological domains. SILs reported in the literature predominantly consist of oligoethers G3 (triglyme) or G4 (tetraglyme) chelating a lithium salt such as LiTFSI/LiTFSA/LiNTf2, lithium bis(trifluoromethanesulphonyl)imide.
{"title":"Solvate ionic liquids: past, present and future","authors":"Timothy Harte, Bhagya Dharmasiri, Žan Simon, David J. Hayne, Daniel J. Eyckens, Luke C. Henderson","doi":"10.1039/d5ta01406a","DOIUrl":"https://doi.org/10.1039/d5ta01406a","url":null,"abstract":"Solvate ionic liquids (SILs) represent an expanding subclass of ionic liquids (ILs), formed through the chelation of the cationic species, typically by an oligoether, and an array of charge diffuse anions. Since their first report, SILs have garnered significant attention for their characteristic ionic liquid physicochemical properties, including high thermal stability, negligible vapour pressure, and tailored solvation dynamics, while being simple to synthesise and cost effective. These factors position SILs as promising candidates for next-generation energy storage applications, including lithium-ion (Li-ion), lithium–sulfur (Li–S), lithium–air (Li–air), lithium-redox, all-solid-state lithium batteries (ASLBs), as well as electric double layer transistors (EDLTs), thermoelectrochemical systems, piezoelectric generators and capacitor/supercapacitor devices. This review traces the evolution of SILs, from foundational studies on their structural and dynamic properties to contemporary advancements in their synthesis and application. SILs modular design potential, through ligand, cation, and anion modifications is evaluated. The multifaceted roles of SILs across various systems are explored, including their applications in electrodeposition and metal extraction, their function as reaction media in organic synthesis, their use as pharmaceutical delivery agents, and their role as constituents and curing catalysts in polymer composites. Furthermore, critical challenges such as optimising ion transport, understanding coordination dynamics, and mitigating environmental impacts are outlined. By integrating experimental insights with computational modeling, this review provides a comprehensive framework to guide future investigations, paving the way for the sustainable development of SILs across scientific and technological domains. SILs reported in the literature predominantly consist of oligoethers G3 (triglyme) or G4 (tetraglyme) chelating a lithium salt such as LiTFSI/LiTFSA/LiNTf<small><sub>2</sub></small>, lithium bis(trifluoromethanesulphonyl)imide.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"72 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766893","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In recent years, single-atom-modified catalysts have emerged as a promising strategy to enhance the efficiency and product selectivity of photocatalytic CO2 reduction. In this work, we systematically investigated Ag single-atom-modified MgAl-LDH using density functional theory (DFT) calculations. Our results demonstrate that the incorporation of Ag single atoms significantly reduces the energy barrier, optimizes the reaction pathway, and ultimately improves CH4 selectivity. The calculated Gibbs free energy changes exhibit a remarkable agreement with the standard theoretical values, with a deviation of only approximately 0.1 eV, highlighting the accuracy and reliability of our computational results. Moreover, our findings further indicate that the active sites for the reactions are situated on the hydroxyl O atoms of the MgAl-LDH adjacent to the Ag atoms, rather than on the Ag atoms themselves. This study offers novel insights and design principles for developing single-atom-modified materials to achieve enhanced CH4 selectivity from a unique perspective.
{"title":"Ag single-atom modification of MgAl-LDH to enhance the CH4 product selectivity in CO2 reduction：A DFT study","authors":"Yi-fu Liu, Feng Yang, Rui-Tang Guo","doi":"10.1039/d5ta01412c","DOIUrl":"https://doi.org/10.1039/d5ta01412c","url":null,"abstract":"In recent years, single-atom-modified catalysts have emerged as a promising strategy to enhance the efficiency and product selectivity of photocatalytic CO2 reduction. In this work, we systematically investigated Ag single-atom-modified MgAl-LDH using density functional theory (DFT) calculations. Our results demonstrate that the incorporation of Ag single atoms significantly reduces the energy barrier, optimizes the reaction pathway, and ultimately improves CH4 selectivity. The calculated Gibbs free energy changes exhibit a remarkable agreement with the standard theoretical values, with a deviation of only approximately 0.1 eV, highlighting the accuracy and reliability of our computational results. Moreover, our findings further indicate that the active sites for the reactions are situated on the hydroxyl O atoms of the MgAl-LDH adjacent to the Ag atoms, rather than on the Ag atoms themselves. This study offers novel insights and design principles for developing single-atom-modified materials to achieve enhanced CH4 selectivity from a unique perspective.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"6 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766887","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Although solid polymer electrolytes (SPEs) hold great promise for high-performance lithium metal batteries (LMBs), the low ionic conductivity and narrow electrochemical window limit their practical application. Herein, we report an ethyl cyanoacrylate (ECA) based semi-interpenetrating polymer network (SIPN) structured SPEs without a traditional solvent removal process. The fabricated deep eutectic solvent (DES) is utilized as both a plasticizer and initiator to trigger the anionic polymerization of ECA to form the linear PECA (DES-PECA). The polymer network formed by copolymerization of poly (ethylene glycol) dimethacrylate and methyl methacrylate is further incorporated to afford the SIPN-based SPEs with lithium difluoro(oxalato)borate as an additive (DESD-SIPN). Benefitting from the unique SIPN structure with a crosslinked polymer network affording mechanical robustness and linear polymer providing high mobility, the DESD-SIPN achieves a decent tensile strength of 1.3 MPa and a high ionic conductivity of 0.139 mS cm-1. The DES and PECA also enable the DESD-SIPN with a voltage stability of up to 4.97 V. Accordingly, the LCO/DESD-SIPN/Li cell stably cycles for 500 times at 1 C and 4.6 V, and the NCM811/DESD-SIPN/Li cell delivers a steady cycling performance at different cutoff voltages of 4.3 V, 4.5 V, and even 4.7 V.
{"title":"Deep eutectic solvent-based semi-interpenetrating polymer electrolyte for high-voltage stable lithium-metal batteries","authors":"Pengfei Cao, Tianhui Cheng, Weixing Min, Mingli Wang, Shuangshuang Zhu, Lengwan Li, Shilun Gao, Zhenxi Li, Jia Tian, Dandan Yang, Huabin Yang","doi":"10.1039/d5ta00020c","DOIUrl":"https://doi.org/10.1039/d5ta00020c","url":null,"abstract":"Although solid polymer electrolytes (SPEs) hold great promise for high-performance lithium metal batteries (LMBs), the low ionic conductivity and narrow electrochemical window limit their practical application. Herein, we report an ethyl cyanoacrylate (ECA) based semi-interpenetrating polymer network (SIPN) structured SPEs without a traditional solvent removal process. The fabricated deep eutectic solvent (DES) is utilized as both a plasticizer and initiator to trigger the anionic polymerization of ECA to form the linear PECA (DES-PECA). The polymer network formed by copolymerization of poly (ethylene glycol) dimethacrylate and methyl methacrylate is further incorporated to afford the SIPN-based SPEs with lithium difluoro(oxalato)borate as an additive (DESD-SIPN). Benefitting from the unique SIPN structure with a crosslinked polymer network affording mechanical robustness and linear polymer providing high mobility, the DESD-SIPN achieves a decent tensile strength of 1.3 MPa and a high ionic conductivity of 0.139 mS cm-1. The DES and PECA also enable the DESD-SIPN with a voltage stability of up to 4.97 V. Accordingly, the LCO/DESD-SIPN/Li cell stably cycles for 500 times at 1 C and 4.6 V, and the NCM811/DESD-SIPN/Li cell delivers a steady cycling performance at different cutoff voltages of 4.3 V, 4.5 V, and even 4.7 V.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"1 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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