Chemistry of Materials最新文献

{"title":"Controlled Growth and Interconversion of Photoluminescent Metal–Organic Frameworks under High-Concentration Conditions","authors":"Tristan A. Pitt, David C. Bain, Mark Del Campo, Andrew J. Musser, Phillip J. Milner","doi":"10.1021/acs.chemmater.5c00355","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00355","url":null,"abstract":"A major drawback to the implementation of metal–organic frameworks (MOFs) on scale is the vast quantity of organic solvents, typically <i>N</i>,<i>N</i>-dimethylformamide (DMF), required to synthesize even small quantities of MOF under traditional dilute (∼0.01 M) solvothermal conditions. High-concentration solvothermal methods offer the opportunity to synthesize MOFs with minimal solvent use but are currently limited by a lack of understanding of how dynamic self-assembly operates under these conditions. Herein, we systematically investigate the crystallization of a series of MOFs under variable concentration (0.01–0.2 M) and temperature (80–160 °C) conditions based on the dilute synthesis of the canonical framework Mg₂(dobdc) (dobdc^4– = 2,5-dioxido-1,4-terephthalate). Through this analysis, we identify controlling factors that lead to isolation of the highly photoluminescent phases Mg(DHT)(DMF)₂ (DHT = dihydroxyterephthalate) and CORN-MOF-1 (Mg) (CORN = Cornell University) or Mg₂(dobdc). Ultimately, we connect the preference for specific MOF phases to the extent of acid-catalyzed DMF hydrolysis and the competing influences of dimethylamine (Me₂NH) and formate (HCO₂^–) at high concentrations, which is likewise affected by temperature, pH, and solvent composition. We use the insights gained to synthesize the Fe, Co, Ni, and Zn analogs of CORN-MOF-1 for the first time, as well as a second series of related MOFs, CORN-MOF-6 (M) (M = Mg, Mn, Fe, Co, Ni), based on the linker 2-hydroxyterephthalic acid (H₃hbdc). Both series exhibit tunable luminescence properties based on the metal composition and crystal structure, making them potentially useful materials for optoelectronic applications. Overall, this work contributes to a clearer understanding of the factors that control MOF formation under high-concentration conditions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"18 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776021","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}

{"title":"Tailoring Potential Ferroelectric Properties in Conformationally Switchable Er(III)-Isothiocyanates Using Organic Cation Modulation","authors":"Rishukumar Panday, Dipti R. Naphade, Anirudh Sowmiyanarayanan, Balu Praveenkumar, Alexander Steiner, Adam Sieradzki, Jan K. Zaręba, Thomas D. Anthopoulos, Ramamoorthy Boomishankar","doi":"10.1021/acs.chemmater.5c00181","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00181","url":null,"abstract":"Hybrid molecular ferroelectrics necessitate switchable components, either organic or inorganic, capable of altering polarity under a reversing electric field. Isothiocyanate (NCS^–) ligands display such behavior through nonlinear coordination with metal ions. Homoleptic complexes of lanthanide ions exhibit variable coordination numbers, which can be controlled by the size of the counterions. We harnessed these properties to achieve polar order and ferroelectricity in hybrid [Er(III)(NCS)_<i>x</i>]^3-x complexes. The incorporation of triethyl methylammonium (<b>TEMA</b>) cations yields the complex <b>[TEMA]</b>_<b>4</b><b>[Er(NCS)</b>_<b>7</b><b>]</b>, which exhibits polarity at low temperatures with a Curie temperature (<i>T</i>_c) of 203 K. Notably, the use of bulkier and more rigid ethyltriphenyl phosphonium (<b>ETPP</b>) cations gave a room-temperature stable ferroelectric complex <b>[ETPP]</b>_<b>3</b><b>[Er(NCS)</b>_<b>6</b><b>]</b>. In contrast, flexible cations, such as tripropylmethylammonium (<b>TPMA</b>), tributylmethylammonium (<b>TBMA</b>), and tetraethyl phosphonium (<b>TEP</b>) ions, yielded only centrosymmetric complexes. The polar structural symmetries in <b>[TEMA]</b>_<b>4</b><b>[Er(NCS)</b>_<b>7</b><b>]</b> and <b>[ETPP]</b>_<b>3</b><b>[Er(NCS)</b>_<b>6</b><b>]</b> are attributed to pronounced distortions of the Er(III)-NCS coordination, driven by the rigid nature of organic counterions. The ferroelectric measurements on <b>[ETPP]</b>_<b>3</b><b>[Er(NCS)</b>_<b>6</b><b>]</b> gave a saturation polarization (<i>P</i>_s) of 1.6 μC cm^–2. Remarkably, <b>[ETPP]</b>_<b>3</b><b>[Er(NCS)</b>_<b>6</b><b>]</b> exhibits a high piezoelectric charge coefficient (<i>d</i>₃₃) of 22.7 pCN^–1 and an electrostrictive coefficient (<i>Q</i>₃₃) of 4.11 m⁴C^–2, enabling its application for piezoelectric energy harvesting.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"17 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766526","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}

{"title":"Direct Visualization of the Dealumination Process on Zeolite Y: How Was the Mesoporous Architecture Formed?","authors":"Yoshihiro Kamimura,&nbsp;Tetsuya Kodaira,&nbsp;Hiroki Yamada,&nbsp;Norihito Hiyoshi and Akira Endo*,&nbsp;","doi":"10.1021/acs.chemmater.4c0323310.1021/acs.chemmater.4c03233","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03233https://doi.org/10.1021/acs.chemmater.4c03233","url":null,"abstract":"<p >The general aspects in the formation mechanism of mesoporous architecture during the dealumination of zeolites are not fully elucidated owing to their complexity, wherein the creation of dealuminated species and pore structural change can occur in diverse ways. In particular, there is still a lack of direct evidence of intermediate states of the mesopore formation, i.e., the detailed location, precise structure, and behavior of the dealuminated species. Herein, integrated techniques of recently developed high-resolution, low-accelerating-voltage field-emission scanning electron microscope (FE-SEM) and energy-dispersive X-ray spectroscopy (EDS) enable direct observation and comparative investigation of the structural and compositional evolution inside zeolite Y with a wide range of Si/Al ratios realized by sequential dealumination. A systematic FE-SEM observation in the cross-section of zeolite Y (fabricated by Ar-BIB milling) revealed that steaming and calcination created a complex local structure in submicrometer-scale regions with bright contrast originating from high-density Al-rich amorphous components. Results of Ar physisorption analyses suggested that steaming and calcination force to eject Al atoms from the zeolite Y framework and create mesopores in it, but this extra-framework Al (EFAl) does not fill micro- and mesopores, which strictly contradicts the previous mechanism. Local condensation of the EFAl leads to a partial collapse of the framework, which transforms into segregated Al-rich amorphous aluminosilicate regions. Further removal of segregated amorphous aluminosilicate via acid leaching significantly led to the additional formation of mesopores. Especially with regard to the internal structure, our concept of the direct visualization approach can be effectively used as a versatile technique to unveil the detailed features of dealuminated species correlated with step-by-step mesopore formation in the dealumination of zeolites.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 8","pages":"2735–2748 2735–2748"},"PeriodicalIF":7.2,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853993","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}

{"title":"Preprocessing Affords 3D Crystalline Poly(3-hexylthiophene) Structure","authors":"Mengting Sun, Zeyuan Sun, Yulong Zheng, Russell Kim, Aaron L. Liu, Lee J. Richter, James F. Gilchrist, Elsa Reichmanis","doi":"10.1021/acs.chemmater.4c03392","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03392","url":null,"abstract":"The aggregation and crystallization of poly(3-hexylthiophene-2,5-diyl) (P3HT), a representative active layer material used for organic field-effect transistor (OFET) applications, are influenced by the solution pretreatment and deposition process. This study explores vibration-assisted convective deposition for the fabrication of OFETs in comparison to spin coating, blade coating, and convective deposition without vibration. The ultraviolet–visible spectroscopic analysis demonstrates that convective deposition, especially assisted with vibration, leads to a greater degree of intrachain interactions, longer conjugation length, and enhanced polymer backbone planarization. When the P3HT solution is preprocessed via sonication and aging, the P3HT films exhibit J-like aggregation, and (h11) peaks can be observed through grazing-incidence wide-angle X-ray scattering, suggesting an ordered 3D crystalline structure. OFETs based on such films exhibit high mobilities (up to 0.14 cm² V^–1 s^–1). The results point to the sensitivity of P3HT charge transport behavior to the intramolecular interactions and backbone planarity and further deepen our understanding of the relationship between processing, aggregates, molecular ordering, and resultant device properties.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"98 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758535","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}

{"title":"Designing Dynamic Hydrogels: The Interplay of Cross-Linker Length, Valency, and Reaction Kinetics in Hydrazone-Based Networks","authors":"Francis L. C. Morgan, Ivo A. O. Beeren, Lorenzo Moroni, Matthew B. Baker","doi":"10.1021/acs.chemmater.4c02573","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02573","url":null,"abstract":"Hydrogels designed using dynamic (reversible) chemistry are prominent tools in diverse research areas as they grant access to time-dependent mechanical properties (self-healing and viscoelasticity), which are inaccessible via purely covalent networks. While the relationship between rate and equilibrium constants (RECs) and bulk mechanical properties is increasingly explored, less known is the effect of network topology or cross-linker length on both REC’s and mechanical properties in dynamically cross-linked hydrogels. Here, we chose hydrazone formation as a model system for dynamic covalent network formation. Using mono- and bivalent hydrazides with molecular weights of 0.1–20 kg·mol^–1, we show that their chemical reactivity with a small molecule aldehyde is largely unaffected by their length. However, the apparent reactivity between two polymeric macromers revealed a decade reduction in <i>k</i>₁ and <i>K</i>_eq compared with the model system. We then studied the impact of different cross-linkers on hydrogel mechanics, revealing a reduction in <i>G</i>′ of 1.3–2.5-fold (cross-linker length) vs 18–28-fold (cross-linker valency), along with emergent strain-stiffening behavior. Finally, we offer potential mechanisms for these observations. These results present a step forward for the rational design of dynamic hydrogel systems with targeted mechanical properties, particularly by facilitating the translation of model studies to practical (macromeric) applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"58 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758597","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}

{"title":"Preprocessing Affords 3D Crystalline Poly(3-hexylthiophene) Structure","authors":"Mengting Sun,&nbsp;Zeyuan Sun,&nbsp;Yulong Zheng,&nbsp;Russell Kim,&nbsp;Aaron L. Liu,&nbsp;Lee J. Richter,&nbsp;James F. Gilchrist and Elsa Reichmanis*,&nbsp;","doi":"10.1021/acs.chemmater.4c0339210.1021/acs.chemmater.4c03392","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03392https://doi.org/10.1021/acs.chemmater.4c03392","url":null,"abstract":"<p >The aggregation and crystallization of poly(3-hexylthiophene-2,5-diyl) (P3HT), a representative active layer material used for organic field-effect transistor (OFET) applications, are influenced by the solution pretreatment and deposition process. This study explores vibration-assisted convective deposition for the fabrication of OFETs in comparison to spin coating, blade coating, and convective deposition without vibration. The ultraviolet–visible spectroscopic analysis demonstrates that convective deposition, especially assisted with vibration, leads to a greater degree of intrachain interactions, longer conjugation length, and enhanced polymer backbone planarization. When the P3HT solution is preprocessed via sonication and aging, the P3HT films exhibit J-like aggregation, and (h11) peaks can be observed through grazing-incidence wide-angle X-ray scattering, suggesting an ordered 3D crystalline structure. OFETs based on such films exhibit high mobilities (up to 0.14 cm² V^–1 s^–1). The results point to the sensitivity of P3HT charge transport behavior to the intramolecular interactions and backbone planarity and further deepen our understanding of the relationship between processing, aggregates, molecular ordering, and resultant device properties.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 8","pages":"2795–2805 2795–2805"},"PeriodicalIF":7.2,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c03392","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Designing Dynamic Hydrogels: The Interplay of Cross-Linker Length, Valency, and Reaction Kinetics in Hydrazone-Based Networks","authors":"Francis L. C. Morgan,&nbsp;Ivo A. O. Beeren,&nbsp;Lorenzo Moroni* and Matthew B. Baker*,&nbsp;","doi":"10.1021/acs.chemmater.4c0257310.1021/acs.chemmater.4c02573","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02573https://doi.org/10.1021/acs.chemmater.4c02573","url":null,"abstract":"<p >Hydrogels designed using dynamic (reversible) chemistry are prominent tools in diverse research areas as they grant access to time-dependent mechanical properties (self-healing and viscoelasticity), which are inaccessible via purely covalent networks. While the relationship between rate and equilibrium constants (RECs) and bulk mechanical properties is increasingly explored, less known is the effect of network topology or cross-linker length on both REC’s and mechanical properties in dynamically cross-linked hydrogels. Here, we chose hydrazone formation as a model system for dynamic covalent network formation. Using mono- and bivalent hydrazides with molecular weights of 0.1–20 kg·mol^–1, we show that their chemical reactivity with a small molecule aldehyde is largely unaffected by their length. However, the apparent reactivity between two polymeric macromers revealed a decade reduction in <i>k</i>₁ and <i>K</i>_eq compared with the model system. We then studied the impact of different cross-linkers on hydrogel mechanics, revealing a reduction in <i>G</i>′ of 1.3–2.5-fold (cross-linker length) vs 18–28-fold (cross-linker valency), along with emergent strain-stiffening behavior. Finally, we offer potential mechanisms for these observations. These results present a step forward for the rational design of dynamic hydrogel systems with targeted mechanical properties, particularly by facilitating the translation of model studies to practical (macromeric) applications.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 8","pages":"2709–2719 2709–2719"},"PeriodicalIF":7.2,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemmater.4c02573","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrolytomics: A Unified Big Data Approach for Electrolyte Design and Discovery","authors":"Ritesh Kumar, Minh Canh Vu, Peiyuan Ma, Chibueze V. Amanchukwu","doi":"10.1021/acs.chemmater.4c03196","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03196","url":null,"abstract":"Electrolyte discovery is the bottleneck for developing next-generation batteries. For example, lithium metal batteries (LMBs) promise to double the energy density of current Li-ion batteries (LIBs), while next-generation LIBs are desired for operations at extreme temperature conditions and with high voltage cathodes. However, there are no suitable electrolytes to support these battery chemistries. Electrolyte requirements are complex (conductivity, stability, safety), and the chemical design space (salts, solvents, additives, concentration) is practically infinite; hence, discovery is primarily guided through trial and error, which slows the deployment of such next-generation battery chemistries. Inspired by artificial intelligence (AI)-enabled drug discovery, we adapt these machine learning (ML) approaches to electrolyte discovery. We assemble the largest small molecule experimental liquid electrolyte ionic conductivity data set and build highly accurate ML and deep learning models to predict ionic conductivity across a wide range of electrolyte classes. The developed models yield results similar to those of molecular dynamics (MD) simulations and are interpretable without explicit encoding of ionic solvation. While most ML-based approaches target a single property, we build additional models of oxidative stability and Coulombic efficiency and develop a metric called the electrolyte score (<i>eScore</i>) to unify the predicted disparate electrolyte properties. Deploying these models on large unlabeled data sets, we discover distinct electrolyte solvents, experimentally validate that the electrolyte is conductive (&gt;1 mS cm^–1), stable up to 6 V, supports efficient anode-free LMB, and even LIB cycling at extreme temperatures. Our work marks a significant step toward efficient electrolyte design, accelerating the development and deployment of next-generation battery technologies.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"38 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745334","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}

{"title":"Electrolytomics: A Unified Big Data Approach for Electrolyte Design and Discovery","authors":"Ritesh Kumar,&nbsp;Minh Canh Vu,&nbsp;Peiyuan Ma and Chibueze V. Amanchukwu*,&nbsp;","doi":"10.1021/acs.chemmater.4c0319610.1021/acs.chemmater.4c03196","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03196https://doi.org/10.1021/acs.chemmater.4c03196","url":null,"abstract":"<p >Electrolyte discovery is the bottleneck for developing next-generation batteries. For example, lithium metal batteries (LMBs) promise to double the energy density of current Li-ion batteries (LIBs), while next-generation LIBs are desired for operations at extreme temperature conditions and with high voltage cathodes. However, there are no suitable electrolytes to support these battery chemistries. Electrolyte requirements are complex (conductivity, stability, safety), and the chemical design space (salts, solvents, additives, concentration) is practically infinite; hence, discovery is primarily guided through trial and error, which slows the deployment of such next-generation battery chemistries. Inspired by artificial intelligence (AI)-enabled drug discovery, we adapt these machine learning (ML) approaches to electrolyte discovery. We assemble the largest small molecule experimental liquid electrolyte ionic conductivity data set and build highly accurate ML and deep learning models to predict ionic conductivity across a wide range of electrolyte classes. The developed models yield results similar to those of molecular dynamics (MD) simulations and are interpretable without explicit encoding of ionic solvation. While most ML-based approaches target a single property, we build additional models of oxidative stability and Coulombic efficiency and develop a metric called the electrolyte score (<i>eScore</i>) to unify the predicted disparate electrolyte properties. Deploying these models on large unlabeled data sets, we discover distinct electrolyte solvents, experimentally validate that the electrolyte is conductive (&gt;1 mS cm^–1), stable up to 6 V, supports efficient anode-free LMB, and even LIB cycling at extreme temperatures. Our work marks a significant step toward efficient electrolyte design, accelerating the development and deployment of next-generation battery technologies.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"37 8","pages":"2720–2734 2720–2734"},"PeriodicalIF":7.2,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143854043","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}

{"title":"Decoding the Three-Card Monte: Unraveling the Role of Solvation Shell, Surface Adsorption, and SEI Formation on Zn Anode Performance","authors":"Bhaskar Kakoty, Disha Brahma, Sreshtha Ganguly, Suraj Halder, Sheetal K. Jain, Sundaram Balasubramanian, Sridhar Rajaram, Premkumar Senguttuvan","doi":"10.1021/acs.chemmater.5c00219","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00219","url":null,"abstract":"Additives or cosolvents are commonly used to curtail parasitic reactions in aqueous Zn-ion batteries. Usually, they are chosen based on the donor number, which indicates their affinity toward Zn²⁺. While their role in the modification of Zn-ion solvation shell, surface adsorption at the electrolyte/anode interface, and formation of solid–electrolyte interphase (SEI) are portrayed as a critical factors for enhancing Zn anode performance, deciphering the individual contributions is important to advance electrolyte engineering. In this work, we unveil the contrasting behaviors of two lactam cosolvents, caprolactam and 2-pyrrolidinone, in aqueous Zn-ion electrolytes. Although both electrolytes exhibit similar Zn-ion solvation structures and double-layer capacitances at the electrode/electrolyte interface, the caprolactam-based electrolyte outperforms its 2-pyrrolidinone counterpart. The Zn|Zn symmetric cell with a caprolactam-based electrolyte renders a cumulative capacity of ∼2600 mAh cm^–2. Time-of-flight secondary-ion mass spectroscopy and <i>in-situ</i> FTIR measurements show the formation of a stable SEI through oligomerization of caprolactam. The importance of stable SEI formation as the key determinant in enhanced performance is further supported by crossover experiments. Overall, this study underscores the paramount importance of stable SEI formation over solvation and adsorption effects in enhancing the lifespan of Zn anodes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"58 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745335","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}