Pub Date : 2025-04-02DOI: 10.1021/acs.chemmater.4c03392
Mengting Sun, Zeyuan Sun, Yulong Zheng, Russell Kim, Aaron L. Liu, Lee J. Richter, James F. Gilchrist, Elsa Reichmanis
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.
{"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 cm<sup>2</sup> V<sup>–1</sup> s<sup>–1</sup>). 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}
Pub Date : 2025-04-02DOI: 10.1021/acs.chemmater.4c02573
Francis L. C. Morgan, Ivo A. O. Beeren, Lorenzo Moroni, Matthew B. Baker
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 k1 and Keq compared with the model system. We then studied the impact of different cross-linkers on hydrogel mechanics, revealing a reduction in G′ 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.
{"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<sup>–1</sup>, 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><sub>1</sub> and <i>K</i><sub>eq</sub> 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}
Pub Date : 2025-04-01DOI: 10.1021/acs.chemmater.4c03196
Ritesh Kumar, Minh Canh Vu, Peiyuan Ma, Chibueze V. Amanchukwu
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 (eScore) 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 (>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.
{"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 (>1 mS cm<sup>–1</sup>), 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}
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 in-situ 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.
{"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 Zn<sup>2+</sup>. 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<sup>–2</sup>. 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}
Pub Date : 2025-03-31DOI: 10.1021/acs.chemmater.5c00028
Taewook Nam, David R. Zywotko, Troy A. Colleran, Jonathan L. Partridge, Steven M. George
Thermal atomic layer etching (ALE) of zinc oxide (ZnO) was demonstrated over a large temperature range from 30–300 °C using sequential exposures of HF (hydrogen fluoride) and Ga(CH3)3 (trimethylgallium (TMG)). In contrast to earlier studies of thermal ZnO ALE using sequential exposures of HF and trimethylaluminum (TMA), ZnO ALE with sequential HF and TMG exposures occurred without competing GaF3 atomic layer deposition (ALD) or ZnO conversion. Quartz crystal microbalance (QCM) studies during ZnO ALE revealed a stepwise mass increase during fluorination by HF exposures and a larger mass decrease during ligand-exchange by TMG exposures. The mass changes per cycle (MCPC) were self-limiting versus HF and TMG exposures at 100 °C. Spectroscopic ellipsometry measured etch rates over a wide temperature range. The etch rates varied from 0.24 Å/cycle at 30 °C to 3.82 Å/cycle at 300 °C. The temperature-dependent etch rates were consistent with an activation barrier of Ea = 3.3 kcal/mol. TMG exposures were also compared with TMA exposures at 100 °C on fresh ZnO surfaces grown by ZnO ALD. TMG exposures led to a mass gain consistent with TMG adsorption. In contrast, TMA exposures produced a mass loss consistent with the conversion of ZnO to Al2O3. Previous studies showed that conversion of ZnO to Al2O3 prevented ZnO ALE using HF and TMA exposures at temperatures less than 205 °C. Etching at <205 °C was restricted because HF adsorption on fluorinated Al2O3 led to competing AlF3 ALD. In contrast, ZnO ALE at temperatures as low as 30 °C is possible because no competing GaF3 ALD occurs using HF and TMG exposures. Quadrupole mass spectrometry (QMS) experiments were also performed to identify the etch products during ZnO ALE. The QMS experiments support fluorination and ligand-exchange reactions without conversion during ZnO ALE using HF and TMG exposures. The HF and TMG exposures were selective for ZnO ALE compared with HfO2, ZrO2 or Al2O3 ALE. ZnO ALE could also smooth ZnO surfaces progressively versus number of ZnO ALE cycles.
{"title":"Thermal Atomic Layer Etching of Zinc Oxide from 30–300 °C Using Sequential Exposures of Hydrogen Fluoride and Trimethylgallium","authors":"Taewook Nam, David R. Zywotko, Troy A. Colleran, Jonathan L. Partridge, Steven M. George","doi":"10.1021/acs.chemmater.5c00028","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00028","url":null,"abstract":"Thermal atomic layer etching (ALE) of zinc oxide (ZnO) was demonstrated over a large temperature range from 30–300 °C using sequential exposures of HF (hydrogen fluoride) and Ga(CH<sub>3</sub>)<sub>3</sub> (trimethylgallium (TMG)). In contrast to earlier studies of thermal ZnO ALE using sequential exposures of HF and trimethylaluminum (TMA), ZnO ALE with sequential HF and TMG exposures occurred without competing GaF<sub>3</sub> atomic layer deposition (ALD) or ZnO conversion. Quartz crystal microbalance (QCM) studies during ZnO ALE revealed a stepwise mass increase during fluorination by HF exposures and a larger mass decrease during ligand-exchange by TMG exposures. The mass changes per cycle (MCPC) were self-limiting versus HF and TMG exposures at 100 °C. Spectroscopic ellipsometry measured etch rates over a wide temperature range. The etch rates varied from 0.24 Å/cycle at 30 °C to 3.82 Å/cycle at 300 °C. The temperature-dependent etch rates were consistent with an activation barrier of <i>E</i><sub>a</sub> = 3.3 kcal/mol. TMG exposures were also compared with TMA exposures at 100 °C on fresh ZnO surfaces grown by ZnO ALD. TMG exposures led to a mass gain consistent with TMG adsorption. In contrast, TMA exposures produced a mass loss consistent with the conversion of ZnO to Al<sub>2</sub>O<sub>3</sub>. Previous studies showed that conversion of ZnO to Al<sub>2</sub>O<sub>3</sub> prevented ZnO ALE using HF and TMA exposures at temperatures less than 205 °C. Etching at <205 °C was restricted because HF adsorption on fluorinated Al<sub>2</sub>O<sub>3</sub> led to competing AlF<sub>3</sub> ALD. In contrast, ZnO ALE at temperatures as low as 30 °C is possible because no competing GaF<sub>3</sub> ALD occurs using HF and TMG exposures. Quadrupole mass spectrometry (QMS) experiments were also performed to identify the etch products during ZnO ALE. The QMS experiments support fluorination and ligand-exchange reactions without conversion during ZnO ALE using HF and TMG exposures. The HF and TMG exposures were selective for ZnO ALE compared with HfO<sub>2</sub>, ZrO<sub>2</sub> or Al<sub>2</sub>O<sub>3</sub> ALE. ZnO ALE could also smooth ZnO surfaces progressively versus number of ZnO ALE cycles.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"183 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745336","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}
Controlling the molecular chirality under external pressure is particularly challenging in low-dimensional hybrid halides, as the constrained structure and strong hydrogen bonding hinder significant conformational changes in bulky organic molecules. Here, by incorporating flexible disulfide-based molecules into the one-dimensional (1D) PbI5 framework, the chiral hybrid halide [NH3(CH2)2S–S(CH2)2NH3]PbI5·H3O undergoes a transformation from conglomerate to racemate at a hydrostatic pressure of approximately 0.10 GPa. This reversible acentric-to-centric transformation is accompanied by the second-harmonic generation (SHG) “on–off” switching and significant conformational changes in the cystamine cations within the structure. In the high-pressure racemic phase, two enantiomers with left- and right-handed conformers (M- and P-helicity) coexist within the lattice structure and their deformations under compression resemble those of a compressed mechanical spring, ultimately leading to considerable distortions of the 1D zigzag PbI5 chains through strong organic–inorganic H···I interactions. Furthermore, both experimental and theoretical results reveal that the unique phase transformation induces minor alterations in the electronic structures and optical bandgaps. Our findings provide insights into the manipulation of molecular chirality and SHG properties in hybrid halides by introducing flexible organic molecules into inorganic frameworks.
{"title":"Pressure-Induced Conglomerate to Racemate Transformation in a One-Dimensional Disulfide-Based Lead Halide","authors":"Wenbo Qiu, Weilong He, Yu Liu, Boyang Fu, Weiyi Wang, Jiangang He, Luhong Wang, Haozhe Liu, Weizhao Cai","doi":"10.1021/acs.chemmater.5c00335","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00335","url":null,"abstract":"Controlling the molecular chirality under external pressure is particularly challenging in low-dimensional hybrid halides, as the constrained structure and strong hydrogen bonding hinder significant conformational changes in bulky organic molecules. Here, by incorporating flexible disulfide-based molecules into the one-dimensional (1D) PbI<sub>5</sub> framework, the chiral hybrid halide [NH<sub>3</sub>(CH<sub>2</sub>)<sub>2</sub>S–S(CH<sub>2</sub>)<sub>2</sub>NH<sub>3</sub>]PbI<sub>5</sub>·H<sub>3</sub>O undergoes a transformation from conglomerate to racemate at a hydrostatic pressure of approximately 0.10 GPa. This reversible acentric-to-centric transformation is accompanied by the second-harmonic generation (SHG) “on–off” switching and significant conformational changes in the cystamine cations within the structure. In the high-pressure racemic phase, two enantiomers with left- and right-handed conformers (M- and P-helicity) coexist within the lattice structure and their deformations under compression resemble those of a compressed mechanical spring, ultimately leading to considerable distortions of the 1D zigzag PbI<sub>5</sub> chains through strong organic–inorganic H···I interactions. Furthermore, both experimental and theoretical results reveal that the unique phase transformation induces minor alterations in the electronic structures and optical bandgaps. Our findings provide insights into the manipulation of molecular chirality and SHG properties in hybrid halides by introducing flexible organic molecules into inorganic frameworks.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"26 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723697","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}
Pub Date : 2025-03-28DOI: 10.1021/acs.chemmater.4c02269
Meaghan M. Deegan, Alexandra M. Antonio, Kyle J. Korman, Andrew A. Ezazi, Kaushalya Korathotage, Merissa N. Morey, Jahidul Hoq, Duleeka Dissanayake, Dewni D. Fernando, Glenn P. A. Yap, David C. Powers, Eric D. Bloch
Metal–organic frameworks (MOFs) have long been explored for their tunable structures and applications in gas separation and catalysis, yet systems capable of engaging in metal-to-ligand π-backbonding remain scarce. Expanding beyond MOFs, our study leverages porous coordination cages (PCCs) as modular building blocks to construct highly tunable porous salts. By incorporating coordinatively unsaturated, π-basic ruthenium sites within charged PCCs, we achieve selective and reversible carbon monoxide chemisorption, a property rarely observed in hybrid porous materials. We further demonstrate that nonporous molecular ruthenium complexes can be incorporated as charge-balancing counterions, yielding materials with tailored porosities and adsorption properties. These findings introduce a strategy for designing porous salts that integrate molecular reactivity with tunable porosity, offering promising avenues for next-generation separations, sensing, and catalysis. Our approach bridges molecular design principles with material functionality, expanding the toolkit for designing adaptive porous materials beyond traditional MOFs.
{"title":"Manipulation of Charged Porous Cages as Tunable Platforms for Strong Gas Adsorption","authors":"Meaghan M. Deegan, Alexandra M. Antonio, Kyle J. Korman, Andrew A. Ezazi, Kaushalya Korathotage, Merissa N. Morey, Jahidul Hoq, Duleeka Dissanayake, Dewni D. Fernando, Glenn P. A. Yap, David C. Powers, Eric D. Bloch","doi":"10.1021/acs.chemmater.4c02269","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02269","url":null,"abstract":"Metal–organic frameworks (MOFs) have long been explored for their tunable structures and applications in gas separation and catalysis, yet systems capable of engaging in metal-to-ligand π-backbonding remain scarce. Expanding beyond MOFs, our study leverages porous coordination cages (PCCs) as modular building blocks to construct highly tunable porous salts. By incorporating coordinatively unsaturated, π-basic ruthenium sites within charged PCCs, we achieve selective and reversible carbon monoxide chemisorption, a property rarely observed in hybrid porous materials. We further demonstrate that nonporous molecular ruthenium complexes can be incorporated as charge-balancing counterions, yielding materials with tailored porosities and adsorption properties. These findings introduce a strategy for designing porous salts that integrate molecular reactivity with tunable porosity, offering promising avenues for next-generation separations, sensing, and catalysis. Our approach bridges molecular design principles with material functionality, expanding the toolkit for designing adaptive porous materials beyond traditional MOFs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723698","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}
Pub Date : 2025-03-27DOI: 10.1021/acs.chemmater.5c00065
Xiang Wang, Sichuang Xue, Xin Qi, Duo Song, Lili Liu, Yatong Zhao, Ping Chen, Maria L. Sushko, Kevin M. Rosso, Xin Zhang
Although significant research has been conducted on metal nanoparticles, a notable gap persists in understanding the fundamental principles governing their crystallization and stability, particularly when deposited on heterogeneous supports. Most current studies focus on specific systems, such as single nanocrystalline facet, which limits the broader understanding of how these processes are influenced by various factors, such as interactions with the facet-dependent crystalline supports. Gaining deeper insights into these mechanisms could lead to the development of more robust and efficient catalytic systems, sensors, and nanomaterials for other advanced applications across various industries. To address this gap, our study focuses on the in-depth examination of the crystallization process of gold (Au) nanoparticles on hematite (104) and (001) facets through in situ transmission electron microscopy (TEM) observation. Our findings reveal the existence of three distinct crystal growth pathways in hematite-supported Au nanoparticles: Ostwald ripening, particle coalescence, and disordered intermediate-phase-mediated growth where particle coalescence plays a dominant role in the sintering process. Furthermore, analysis of crystal growth kinetics on different facets of hematite substrate highlights a facet-dependent behavior. Hematite (001) effectively stabilizes Au nanoparticles and suppresses their sintering more effectively than (104) facets. This enhanced stabilization is attributed to the lower surface energy and stronger interaction between Au and the hematite (001) facet. Density functional theory (DFT) calculations, in conjunction with molecular dynamics (MD) simulations, provide valuable insight into heterogeneous coarsening of Au nanoparticles on hematite. Our research significantly contributes to the understanding of facet-dependent growth of metal nanoparticles on hematite nanocrystals and offers guidelines for selecting hematite-supported heterogeneous catalysts.
{"title":"In-Situ Study of Heterogeneous Crystal Growth of Gold Nanoparticles on Hematite Facets","authors":"Xiang Wang, Sichuang Xue, Xin Qi, Duo Song, Lili Liu, Yatong Zhao, Ping Chen, Maria L. Sushko, Kevin M. Rosso, Xin Zhang","doi":"10.1021/acs.chemmater.5c00065","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00065","url":null,"abstract":"Although significant research has been conducted on metal nanoparticles, a notable gap persists in understanding the fundamental principles governing their crystallization and stability, particularly when deposited on heterogeneous supports. Most current studies focus on specific systems, such as single nanocrystalline facet, which limits the broader understanding of how these processes are influenced by various factors, such as interactions with the facet-dependent crystalline supports. Gaining deeper insights into these mechanisms could lead to the development of more robust and efficient catalytic systems, sensors, and nanomaterials for other advanced applications across various industries. To address this gap, our study focuses on the in-depth examination of the crystallization process of gold (Au) nanoparticles on hematite (104) and (001) facets through in situ transmission electron microscopy (TEM) observation. Our findings reveal the existence of three distinct crystal growth pathways in hematite-supported Au nanoparticles: Ostwald ripening, particle coalescence, and disordered intermediate-phase-mediated growth where particle coalescence plays a dominant role in the sintering process. Furthermore, analysis of crystal growth kinetics on different facets of hematite substrate highlights a facet-dependent behavior. Hematite (001) effectively stabilizes Au nanoparticles and suppresses their sintering more effectively than (104) facets. This enhanced stabilization is attributed to the lower surface energy and stronger interaction between Au and the hematite (001) facet. Density functional theory (DFT) calculations, in conjunction with molecular dynamics (MD) simulations, provide valuable insight into heterogeneous coarsening of Au nanoparticles on hematite. Our research significantly contributes to the understanding of facet-dependent growth of metal nanoparticles on hematite nanocrystals and offers guidelines for selecting hematite-supported heterogeneous catalysts.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"125 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713784","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}
Flexible polymeric solid–solid phase change materials (PCMs) have garnered continuous attention owing to their potential for thermal management in flexible/wearable devices and their non-leakage characteristics. However, it is still a big challenge to obtain polymeric solid–solid PCMs with both flexibility and high latent heat. In this study, bottlebrush phase change polysiloxane networks with alkyl side chains of different lengths (Si-X) are prepared through a one-step grafting cross-linking process. The influence of the length of the grafting chain on the mechanical and thermomechanical properties, phase change behavior, rheological characteristics, and thermal stability of materials is systematically studied. Furthermore, the concept of progressive phase change is proposed by cografting of crystalline side chains with multiple lengths in bottlebrush polysiloxane networks, which reduces the dense packing of crystals. The resulting network (Si-ODDT-70) exhibits excellent latent heat (ΔHm = 128.0 J/g; ΔHf = 129.1 J/g) and elongation at break values exceeding 200 and 450% at room and body temperatures, respectively. In addition, Si-ODDT-70 can be freely coiled, rolled, cut, and repaired with UV light at room temperature. Besides, the recyclable, stretchable/bendable, and multiresponsive phase change composites are obtained by combining the liquid metal/graphene paper with Si-ODDT-70. The first proposed cografting strategy offers a solution to unify the flexibility and high latent heat of PCMs, which will further enrich bottlebrush polymer network topology structures and guide the future design of flexible polymeric PCMs.
{"title":"Wearable Thermal Energy Storage Polymeric Materials via the Progressive Phase Change Strategy of Crystalline Bottlebrush Polysiloxane Networks","authors":"Jiahao Ma, Tian Ma, Yanyun Li, Qiguang Liu, Jue Cheng, Junying Zhang","doi":"10.1021/acs.chemmater.5c00005","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00005","url":null,"abstract":"Flexible polymeric solid–solid phase change materials (PCMs) have garnered continuous attention owing to their potential for thermal management in flexible/wearable devices and their non-leakage characteristics. However, it is still a big challenge to obtain polymeric solid–solid PCMs with both flexibility and high latent heat. In this study, bottlebrush phase change polysiloxane networks with alkyl side chains of different lengths (Si-X) are prepared through a one-step grafting cross-linking process. The influence of the length of the grafting chain on the mechanical and thermomechanical properties, phase change behavior, rheological characteristics, and thermal stability of materials is systematically studied. Furthermore, the concept of progressive phase change is proposed by cografting of crystalline side chains with multiple lengths in bottlebrush polysiloxane networks, which reduces the dense packing of crystals. The resulting network (Si-ODDT-70) exhibits excellent latent heat (Δ<i>H</i><sub>m</sub> = 128.0 J/g; Δ<i>H</i><sub>f</sub> = 129.1 J/g) and elongation at break values exceeding 200 and 450% at room and body temperatures, respectively. In addition, Si-ODDT-70 can be freely coiled, rolled, cut, and repaired with UV light at room temperature. Besides, the recyclable, stretchable/bendable, and multiresponsive phase change composites are obtained by combining the liquid metal/graphene paper with Si-ODDT-70. The first proposed cografting strategy offers a solution to unify the flexibility and high latent heat of PCMs, which will further enrich bottlebrush polymer network topology structures and guide the future design of flexible polymeric PCMs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"59 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723699","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}
Pub Date : 2025-03-27DOI: 10.1021/acs.chemmater.5c00016
Vellaichamy Joseph, Keiichiro Maegawa, Mateusz Wlazło, Marek J. Potrzebowski, Krzysztof Łyczko, Atsushi Nagai
An organic salt (DMAP/Pa-SO3H) composed of 2,5-diaminiobenzenesulfonic acid (Pa-SO3H) and dimethylaminopyridine (DMAP) was demonstrated as a linker to construct ionic covalent organic frameworks (iCOFs). The iCOF denoted as TpDMAP/Pa-SO3H was prepared by the condensation reaction of the triformylphloroglucinol (Tp) building block and DMAP/Pa-SO3H and offers the potential to accommodate an external proton source (H3PO4; PA), enabling the immobilization of PA moieties within the pore structure through a strong ionic hydrogen bonding interaction evidenced by DFT calculations. Furthermore, H3PO4-doped iCOF denoted as PA@TpDMAP/Pa-SO3H proclaimed the advantage of engineering at the linker position, which in turn promotes proton conductivity to 1.56 × 10–2 S cm–1 (increased 100-fold as related to PA@TpPa-SO3H) at 140 °C under anhydrous conditions. Finally, we investigated the adaptability of a dual-acid system in sulfonated poly(ether ether ketone) (SPEEK) membranes, a common acid-modified polymeric material. PA-doped DMAP-modified SPEEK (PA@SPEEK/DMAP) evidenced a 100-fold appreciation of proton conductivity at 120 °C, as compared to bare SPEEK membranes under anhydrous conditions.
{"title":"Dual-Acid-Tailored Ionic Covalent Organic Frameworks for High-Temperature Proton Conduction under Anhydrous Conditions and the Practical Opportunities","authors":"Vellaichamy Joseph, Keiichiro Maegawa, Mateusz Wlazło, Marek J. Potrzebowski, Krzysztof Łyczko, Atsushi Nagai","doi":"10.1021/acs.chemmater.5c00016","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00016","url":null,"abstract":"An organic salt (DMAP/Pa-SO<sub>3</sub>H) composed of 2,5-diaminiobenzenesulfonic acid (Pa-SO<sub>3</sub>H) and dimethylaminopyridine (DMAP) was demonstrated as a linker to construct ionic covalent organic frameworks (iCOFs). The iCOF denoted as TpDMAP/Pa-SO<sub>3</sub>H was prepared by the condensation reaction of the triformylphloroglucinol (Tp) building block and DMAP/Pa-SO<sub>3</sub>H and offers the potential to accommodate an external proton source (H<sub>3</sub>PO<sub>4</sub>; PA), enabling the immobilization of PA moieties within the pore structure through a strong ionic hydrogen bonding interaction evidenced by DFT calculations. Furthermore, H<sub>3</sub>PO<sub>4</sub>-doped iCOF denoted as PA@TpDMAP/Pa-SO<sub>3</sub>H proclaimed the advantage of engineering at the linker position, which in turn promotes proton conductivity to 1.56 × 10<sup>–2</sup> S cm<sup>–1</sup> (increased 100-fold as related to PA@TpPa-SO<sub>3</sub>H) at 140 °C under anhydrous conditions. Finally, we investigated the adaptability of a dual-acid system in sulfonated poly(ether ether ketone) (SPEEK) membranes, a common acid-modified polymeric material. PA-doped DMAP-modified SPEEK (PA@SPEEK/DMAP) evidenced a 100-fold appreciation of proton conductivity at 120 °C, as compared to bare SPEEK membranes under anhydrous conditions.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"57 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713783","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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