Metal–covalent organic frameworks (MCOFs) combining the advantages of open metal sites of metal–organic frameworks and covalent connections of COFs are potential platform for gas separation. Herein, three 2D cuprous-based MCOFs (Cu-COFs, named Cu-TABA, Cu-TFBA, and Cu-TP) are designed and synthesized through Schiff base condensation using two trinuclear cuprous complexes and three organic building blocks with different sizes. These Cu-COFs possess high crystallinity, good stability, and microporous structure with gradually decreasing pore size. The 1D columnar channels facilitate the rapid transport of gas molecules along the layer-by-layer stacking direction. The open cuprous ions serve as adsorption sites and interact strongly with propylene (C3H6) through π-complexation. The mixed matrix membranes (MMMs) fabricated by Cu-COFs and polymer (6FDA-DAM) exhibit superior propylene/propane (C3H6/C3H8) separation performance; shown by C3H6 permeability as high as 85.5 Barrer and C3H6/C3H8 selectivity reaching 36.6, much higher than those of pure 6FDA-DAM membrane. The performance beyond most reported MMMs demonstrates that Cu-COFs are candidate membrane materials for C3H6/C3H8 separation.
{"title":"Synthesis of Cuprous Organic Frameworks with Adjustable Pores as Membrane Materials for C3H6/C3H8 Separation","authors":"Zeliang Cheng, Hui Wu, Hao Zhang, Ziyang Wang, Lina Wang, Xiaoqin Zou, Guangshan Zhu","doi":"10.1002/sstr.202400295","DOIUrl":"https://doi.org/10.1002/sstr.202400295","url":null,"abstract":"Metal–covalent organic frameworks (MCOFs) combining the advantages of open metal sites of metal–organic frameworks and covalent connections of COFs are potential platform for gas separation. Herein, three 2D cuprous-based MCOFs (Cu-COFs, named Cu-TABA, Cu-TFBA, and Cu-TP) are designed and synthesized through Schiff base condensation using two trinuclear cuprous complexes and three organic building blocks with different sizes. These Cu-COFs possess high crystallinity, good stability, and microporous structure with gradually decreasing pore size. The 1D columnar channels facilitate the rapid transport of gas molecules along the layer-by-layer stacking direction. The open cuprous ions serve as adsorption sites and interact strongly with propylene (C<sub>3</sub>H<sub>6</sub>) through <i>π</i>-complexation. The mixed matrix membranes (MMMs) fabricated by Cu-COFs and polymer (6FDA-DAM) exhibit superior propylene/propane (C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub>) separation performance; shown by C<sub>3</sub>H<sub>6</sub> permeability as high as 85.5 Barrer and C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> selectivity reaching 36.6, much higher than those of pure 6FDA-DAM membrane. The performance beyond most reported MMMs demonstrates that Cu-COFs are candidate membrane materials for C<sub>3</sub>H<sub>6</sub>/C<sub>3</sub>H<sub>8</sub> separation.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"33 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Indirajith Palani, Duyen Thi Nguyen, Jongchan Kim, Quang Khanh Nguyen, Long Van Nguyen, Da Som Song, Jong Sun Lim, Chang Gyon Kim, Kyeongjae Cho, Myung Mo Sung
Thermoelectric materials play a crucial role in converting heat into electricity, offering significant potential for applications in waste heat recovery and cooling. Herein, an innovative approach that combines an organic–inorganic hybrid superlattice structure with nanocrystal-amorphous composite nanolayers is introduced. The nanocrystal-amorphous composite enhances the Seebeck coefficient resulting in a notable twofold improvement in the power factor. The superlattice, alternating self-assembled organic monolayers and inorganic nanolayers, effectively reduces lattice thermal conductivity by creating multiple interfaces that scatter phonons effectively. The integration of the nanocrystal-amorphous composite nanolayers into the superlattice provides a dual advantage, simultaneously boosting the power factor and suppressing thermal conductivity. This synergistic effect leads to exceptional thermoelectric performance in the 4-mercaptophenol/Sb2Te3 superlattice, with achieved figure of merit (ZT) values of 3.48 at 300 K and reaching a peak ZT value exceeding 4.0 at 400 K while surpassing 2.5 over the temperature range from 300 to 500 K. These results suggest that this innovative approach paves the way for the development of highly efficient thermoelectric materials, propelling efforts toward more energy-efficient and environmentally friendly solutions.
热电材料在将热能转化为电能方面发挥着至关重要的作用，为废热回收和冷却领域的应用提供了巨大潜力。本文介绍了一种将有机-无机混合超晶格结构与纳米晶体-非晶态复合纳米层相结合的创新方法。纳米晶体-非晶态复合材料提高了塞贝克系数，使功率因数显著提高了两倍。超晶格是自组装有机单层和无机纳米层的交替层，通过形成能有效散射声子的多个界面，有效降低了晶格热导率。将纳米晶体-非晶态复合纳米层集成到超晶格中具有双重优势，既能提高功率因数，又能抑制热导率。这种协同效应使 4-巯基酚/Sb2Te3 超晶格具有卓越的热电性能，在 300 K 时达到 3.48 的优越性（ZT）值，在 400 K 时达到超过 4.0 的 ZT 峰值，而在 300 至 500 K 的温度范围内超过 2.5。
{"title":"An Organic–Inorganic Superlattice with Nanocrystal-Amorphous Composite Nanolayers for Ultrahigh Thermoelectric Performance","authors":"Indirajith Palani, Duyen Thi Nguyen, Jongchan Kim, Quang Khanh Nguyen, Long Van Nguyen, Da Som Song, Jong Sun Lim, Chang Gyon Kim, Kyeongjae Cho, Myung Mo Sung","doi":"10.1002/sstr.202400201","DOIUrl":"https://doi.org/10.1002/sstr.202400201","url":null,"abstract":"Thermoelectric materials play a crucial role in converting heat into electricity, offering significant potential for applications in waste heat recovery and cooling. Herein, an innovative approach that combines an organic–inorganic hybrid superlattice structure with nanocrystal-amorphous composite nanolayers is introduced. The nanocrystal-amorphous composite enhances the Seebeck coefficient resulting in a notable twofold improvement in the power factor. The superlattice, alternating self-assembled organic monolayers and inorganic nanolayers, effectively reduces lattice thermal conductivity by creating multiple interfaces that scatter phonons effectively. The integration of the nanocrystal-amorphous composite nanolayers into the superlattice provides a dual advantage, simultaneously boosting the power factor and suppressing thermal conductivity. This synergistic effect leads to exceptional thermoelectric performance in the 4-mercaptophenol/Sb<sub>2</sub>Te<sub>3</sub> superlattice, with achieved figure of merit (ZT) values of 3.48 at 300 K and reaching a peak ZT value exceeding 4.0 at 400 K while surpassing 2.5 over the temperature range from 300 to 500 K. These results suggest that this innovative approach paves the way for the development of highly efficient thermoelectric materials, propelling efforts toward more energy-efficient and environmentally friendly solutions.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"195 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ye Zhang, Siting Chen, Shihua Luo, Wenbin Li, Lifeng Zhang, Fei Lan, Yitong Zhu, Huijun Du, Ke Li, Chunchen Liu, Bo Situ, Bo Li, Xiaohui Yan
The utility of circular RNAs (circRNAs) as emerging biomarkers and regulatory factors in medical diagnostics and therapeutics is hampered by the challenges associated with their sensitive detection and precise modulation. Herein, a high-performance cooperative DNA nanodevice (HCDN) based on DNA tetrahedron-confined catalytic DNA assembly reaction (DT-CDA) that enables both imaging and regulation of circRNAs is developed. Activation of the DT-CDA is contingent upon the presence of the target circRNA, which, together with a replicative fuel probe, catalyzes the sequential opening of additional DT-CDAs. This cooperative exponential signal amplification with negligible background interference allows HCDN to effectively detect minute quantities of circRNAs. Employing circSATB2 as a model, the HCDN demonstrates substantial downregulation of Cyclin D1 (CCND1) mRNA and protein levels in cellular and in vivo models, thereby inhibiting tumor growth. The innovative design of HCDN sets the stage for a powerful methodology conducive to enhanced clinical diagnostics and biomolecule manipulation, thereby advancing the capabilities and applications of DNA nanotechnology.
{"title":"High-Performance Cooperative DNA Nanodevice Enables Sensitive Circular RNA Imaging and Precise Tumor Growth Suppression","authors":"Ye Zhang, Siting Chen, Shihua Luo, Wenbin Li, Lifeng Zhang, Fei Lan, Yitong Zhu, Huijun Du, Ke Li, Chunchen Liu, Bo Situ, Bo Li, Xiaohui Yan","doi":"10.1002/sstr.202400255","DOIUrl":"https://doi.org/10.1002/sstr.202400255","url":null,"abstract":"The utility of circular RNAs (circRNAs) as emerging biomarkers and regulatory factors in medical diagnostics and therapeutics is hampered by the challenges associated with their sensitive detection and precise modulation. Herein, a high-performance cooperative DNA nanodevice (HCDN) based on DNA tetrahedron-confined catalytic DNA assembly reaction (DT-CDA) that enables both imaging and regulation of circRNAs is developed. Activation of the DT-CDA is contingent upon the presence of the target circRNA, which, together with a replicative fuel probe, catalyzes the sequential opening of additional DT-CDAs. This cooperative exponential signal amplification with negligible background interference allows HCDN to effectively detect minute quantities of circRNAs. Employing circSATB2 as a model, the HCDN demonstrates substantial downregulation of Cyclin D1 (CCND1) mRNA and protein levels in cellular and in vivo models, thereby inhibiting tumor growth. The innovative design of HCDN sets the stage for a powerful methodology conducive to enhanced clinical diagnostics and biomolecule manipulation, thereby advancing the capabilities and applications of DNA nanotechnology.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"59 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935914","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marco Joes Lüther, Shi-Kai Jiang, Martin Alexander Lange, Julius Buchmann, Aurora Gómez Martín, Richard Schmuch, Tobias Placke, Bing Joe Hwang, Martin Winter, Johannes Kasnatscheew
State-of-the-art ternary layered oxide cathode active materials in Li-ion batteries (LIBs) consist of polycrystalline (PC), i.e., micron-sized secondary particles, which in turn consist of numerous nanosized primary particles. Recent approaches to develop single crystals (SCs), i.e., single and separated micron-sized primary particles, appear promising in terms of cycle life given their mechanical stability. However, a direct and systematic (“fair”) comparison of SC with PC in LIB cell application remains a challenge due to both differences on material level and state-of-charge (SoC), as SCs typically have slightly lower delithiation capacities/Li+ extraction ratios. In this work, PC and SC Li[Ni0.8Mn0.1Co0.1]O2 (NMC811) are synthesized with comparable bulk and surface characteristics from identical self-synthesized precursors. Indeed, the cycle life of SCs is not only superior, when conventionally charged to equal upper cutoff voltage (UCV), as shown in NMC||Li and NMC||graphite cells, but also after adjusting UCVs to similar SoCs, where bigger SCs counterintuitively have even a better rate performance and cycle life.
{"title":"Systematic “Apple-to-Apple” Comparison of Single-Crystal and Polycrystalline Ni-Rich Cathode Active Materials: From Comparable Synthesis to Comparable Electrochemical Conditions","authors":"Marco Joes Lüther, Shi-Kai Jiang, Martin Alexander Lange, Julius Buchmann, Aurora Gómez Martín, Richard Schmuch, Tobias Placke, Bing Joe Hwang, Martin Winter, Johannes Kasnatscheew","doi":"10.1002/sstr.202400119","DOIUrl":"https://doi.org/10.1002/sstr.202400119","url":null,"abstract":"State-of-the-art ternary layered oxide cathode active materials in Li-ion batteries (LIBs) consist of polycrystalline (PC), i.e., micron-sized secondary particles, which in turn consist of numerous nanosized primary particles. Recent approaches to develop single crystals (SCs), i.e., single and separated micron-sized primary particles, appear promising in terms of cycle life given their mechanical stability. However, a direct and systematic (“fair”) comparison of SC with PC in LIB cell application remains a challenge due to both differences on material level and state-of-charge (SoC), as SCs typically have slightly lower delithiation capacities/Li<sup>+</sup> extraction ratios. In this work, PC and SC Li[Ni<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>]O<sub>2</sub> (NMC811) are synthesized with comparable bulk and surface characteristics from identical self-synthesized precursors. Indeed, the cycle life of SCs is not only superior, when conventionally charged to equal upper cutoff voltage (UCV), as shown in NMC||Li and NMC||graphite cells, but also after adjusting UCVs to similar SoCs, where bigger SCs counterintuitively have even a better rate performance and cycle life.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"22 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
John M. McBride, Aleksei Koshevarnikov, Marta Siek, Bartosz A. Grzybowski, Tsvi Tlusty
Despite recent breakthroughs in understanding how protein sequence relates to structure and function, considerably less attention has been paid to the general features of protein surfaces beyond those regions involved in binding and catalysis. This article provides a systematic survey of the universe of protein surfaces and quantifies the sizes, shapes, and curvatures of the positively/negatively charged and hydrophobic/hydrophilic surface patches as well as correlations between such patches. It then compares these statistics with the metrics characterizing nanoparticles functionalized with ligands terminated with positively and negatively charged ligands. These particles are of particular interest because they are also surface patchy and have been shown to exhibit both antibiotic and anticancer activities—via selective interactions against various cellular structures—prompting loose analogies to proteins. The analyses support such analogies in several respects (e.g., patterns of charged protrusions and hydrophobic niches similar to those observed in proteins), although there are also significant differences. Looking forward, this work provides a blueprint for the rational design of synthetic nano-objects with further enhanced mimicry of proteins’ surface properties.
{"title":"Statistical Survey of Chemical and Geometric Patterns on Protein Surfaces as a Blueprint for Protein-Mimicking Nanoparticles","authors":"John M. McBride, Aleksei Koshevarnikov, Marta Siek, Bartosz A. Grzybowski, Tsvi Tlusty","doi":"10.1002/sstr.202400086","DOIUrl":"https://doi.org/10.1002/sstr.202400086","url":null,"abstract":"Despite recent breakthroughs in understanding how protein sequence relates to structure and function, considerably less attention has been paid to the general features of protein surfaces beyond those regions involved in binding and catalysis. This article provides a systematic survey of the universe of protein surfaces and quantifies the sizes, shapes, and curvatures of the positively/negatively charged and hydrophobic/hydrophilic surface patches as well as correlations between such patches. It then compares these statistics with the metrics characterizing nanoparticles functionalized with ligands terminated with positively and negatively charged ligands. These particles are of particular interest because they are also surface patchy and have been shown to exhibit both antibiotic and anticancer activities—via selective interactions against various cellular structures—prompting loose analogies to proteins. The analyses support such analogies in several respects (e.g., patterns of charged protrusions and hydrophobic niches similar to those observed in proteins), although there are also significant differences. Looking forward, this work provides a blueprint for the rational design of synthetic nano-objects with further enhanced mimicry of proteins’ surface properties.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"43 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935917","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jiayue Sun, Birk Fritsch, Andreas Körner, Mehran Taherkhani, Chiwoo Park, Mei Wang, Andreas Hutzler, Taylor J. Woehl
Formation kinetics of metal nanoparticles are generally described via mass transport and thermodynamics-based models, such as diffusion-limited growth and classical nucleation theory (CNT). However, metal monomers are commonly assumed as precursors, leaving the identity of molecular intermediates and their contribution to nanoparticle formation unclear. Herein, liquid phase transmission electron microscopy (LPTEM) and reaction kinetic modeling are utilized to establish the nucleation and growth mechanisms and discover molecular intermediates during silver nanoparticle formation. Quantitative LPTEM measurements show that their nucleation rate decreases while growth rate is nearly invariant with electron dose rate. Reaction kinetic simulations show that Ag4 and Ag− follow a statistically similar dose rate dependence as the experimentally determined growth rate. We show that experimental growth rates are consistent with diffusion-limited growth via the attachment of these species to nanoparticles. The dose rate dependence of nucleation rate is inconsistent with CNT. A reaction-limited nucleation mechanism is proposed and it is demonstrated that experimental nucleation kinetics are consistent with Ag42+ aggregation rates at millisecond time scales. Reaction throughput analysis of the kinetic simulations uncovered formation and decay pathways mediating intermediate concentrations. We demonstrate the power of quantitative LPTEM combined with kinetic modeling for establishing nanoparticle formation mechanisms and principal intermediates.
{"title":"Discovery of Molecular Intermediates and Nonclassical Nanoparticle Formation Mechanisms by Liquid Phase Electron Microscopy and Reaction Throughput Analysis","authors":"Jiayue Sun, Birk Fritsch, Andreas Körner, Mehran Taherkhani, Chiwoo Park, Mei Wang, Andreas Hutzler, Taylor J. Woehl","doi":"10.1002/sstr.202400146","DOIUrl":"https://doi.org/10.1002/sstr.202400146","url":null,"abstract":"Formation kinetics of metal nanoparticles are generally described <i>via</i> mass transport and thermodynamics-based models, such as diffusion-limited growth and classical nucleation theory (CNT). However, metal monomers are commonly assumed as precursors, leaving the identity of molecular intermediates and their contribution to nanoparticle formation unclear. Herein, liquid phase transmission electron microscopy (LPTEM) and reaction kinetic modeling are utilized to establish the nucleation and growth mechanisms and discover molecular intermediates during silver nanoparticle formation. Quantitative LPTEM measurements show that their nucleation rate decreases while growth rate is nearly invariant with electron dose rate. Reaction kinetic simulations show that Ag<sub>4</sub> and Ag<sup>−</sup> follow a statistically similar dose rate dependence as the experimentally determined growth rate. We show that experimental growth rates are consistent with diffusion-limited growth <i>via</i> the attachment of these species to nanoparticles. The dose rate dependence of nucleation rate is inconsistent with CNT. A reaction-limited nucleation mechanism is proposed and it is demonstrated that experimental nucleation kinetics are consistent with Ag<sub>4</sub><sup>2+</sup> aggregation rates at millisecond time scales. Reaction throughput analysis of the kinetic simulations uncovered formation and decay pathways mediating intermediate concentrations. We demonstrate the power of quantitative LPTEM combined with kinetic modeling for establishing nanoparticle formation mechanisms and principal intermediates.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"3 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks have recently emerged as nonlinear optical (NLO) materials for potential applications in optics. However, the chemistry for designing third-order NLO 2DP films with large nonlinear absorption coefficient (β) has remained a mystery. Herein, three highly crystalline porphyrin-integrated 2D polyimines (named as 2DPI-Zn-Azo, 2DPI-2H-Azo, and 2DPI-Zn), which are homogeneous films showing large lateral areas over cm2, uniform transparency, and thickness of tens of nanometers are reported. Particularly, the 2DPI-Zn-Azo film comprising zinc porphyrin and –NN– displays a large saturable absorption under 532 nm and the highest β (−1.88 × 105 cm GW−1) among the three 2D polyimines, that is also 2–5 orders of magnitude higher than the state-of-art performance of photoactive small molecules, porphyrin-integrated 2DPs, and inorganic 2D materials. Control experiments in combination with theoretical calculation discover that the embedding of metal centers and –NN– results in highly delocalized π-electrons and narrow bandgap in 2DPI-Zn-Azo, which enables fast transfer of the photogenerated electrons after the light-excited charge separation, thus boosting the NLO performance. This work opens up a new path for the construction of highly efficient third-order NLO film materials, and pushes the development of 2DPs for optics and optoelectronics.
{"title":"Interfacial Synthesis of Two-Dimensional Porphyrin Polymer Films with Large Optical Nonlinearity","authors":"Fengxiang Zhao, Geping Zhang, Wei Xie, Xin Kong, Xiaomeng Duan, Yubin Fu, Jichao Zhang, Guoquan Gao, Tong Zhu, Jingcheng Hao, Hongguang Li, Renhao Dong","doi":"10.1002/sstr.202400152","DOIUrl":"https://doi.org/10.1002/sstr.202400152","url":null,"abstract":"Two-dimensional polymers (2DPs) and their layer-stacked 2D covalent organic frameworks have recently emerged as nonlinear optical (NLO) materials for potential applications in optics. However, the chemistry for designing third-order NLO 2DP films with large nonlinear absorption coefficient (<i>β</i>) has remained a mystery. Herein, three highly crystalline porphyrin-integrated 2D polyimines (named as 2DPI-Zn-Azo, 2DPI-2H-Azo, and 2DPI-Zn), which are homogeneous films showing large lateral areas over cm<sup>2</sup>, uniform transparency, and thickness of tens of nanometers are reported. Particularly, the 2DPI-Zn-Azo film comprising zinc porphyrin and –NN– displays a large saturable absorption under 532 nm and the highest <i>β</i> (−1.88 × 10<sup>5</sup> cm GW<sup>−1</sup>) among the three 2D polyimines, that is also 2–5 orders of magnitude higher than the state-of-art performance of photoactive small molecules, porphyrin-integrated 2DPs, and inorganic 2D materials. Control experiments in combination with theoretical calculation discover that the embedding of metal centers and –NN– results in highly delocalized <i>π</i>-electrons and narrow bandgap in 2DPI-Zn-Azo, which enables fast transfer of the photogenerated electrons after the light-excited charge separation, thus boosting the NLO performance. This work opens up a new path for the construction of highly efficient third-order NLO film materials, and pushes the development of 2DPs for optics and optoelectronics.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"683 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141873396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pedram Ghorbanzade, Arianna Pesce, Michel Armand, Kerman Gómez, Shanmukaraj Devaraj, Pedro López-Aranguren, Juan Miguel López del Amo
Li6PS5Cl (LPSCl) argyrodites offer high room temperature ionic conductivity (>1 mS cm−1) and are among the most promising solid electrolytes. However, their chemical instability against Li metal compromises the long-term cyclability. Using PEO-LiTFSI as an interlayer or as a matrix for composite electrolytes is a promising strategy to address this issue. Nevertheless, the interphase of PEO-LiTFSI and LPSCl requires further detailed investigations. This work explores the interfacial reactions between these phases using solid-state nuclear magnetic resonance. Results show that PEO facilitates the formation of a complex with LiCl and Li3PS4 from LPSCl, resulting in an interphase material with limited local mobility, thus impeding ion transport. Although the addition of Br as a dopant can improve the ionic conductivity of LPSCl by inducing disorder and generating the Li vacancies, it makes the LPSCl more susceptible to PEO and increases the extent of the interfacial reaction. 6Li–6Li EXSY experiments demonstrate spontaneous Li-ion exchange between the PEO and the LPSCl, yet this exchange is significantly hindered by reaction products within the PEO-LPSCl interphase, attributable to their sluggish local dynamics. This study sheds light on the complex interfacial interaction between PEO-LiTFSI and sulfide argyrodite, providing insights into designing solid electrolytes for the new generation of electrochemical devices.
{"title":"Unveiling the Reactivity and the Li-Ion Exchange at the PEO-Li6PS5Cl Interphase: Insights from Solid-State NMR","authors":"Pedram Ghorbanzade, Arianna Pesce, Michel Armand, Kerman Gómez, Shanmukaraj Devaraj, Pedro López-Aranguren, Juan Miguel López del Amo","doi":"10.1002/sstr.202400139","DOIUrl":"https://doi.org/10.1002/sstr.202400139","url":null,"abstract":"Li<sub>6</sub>PS<sub>5</sub>Cl (LPSCl) argyrodites offer high room temperature ionic conductivity (>1 mS cm<sup>−1</sup>) and are among the most promising solid electrolytes. However, their chemical instability against Li metal compromises the long-term cyclability. Using PEO-LiTFSI as an interlayer or as a matrix for composite electrolytes is a promising strategy to address this issue. Nevertheless, the interphase of PEO-LiTFSI and LPSCl requires further detailed investigations. This work explores the interfacial reactions between these phases using solid-state nuclear magnetic resonance. Results show that PEO facilitates the formation of a complex with LiCl and Li<sub>3</sub>PS<sub>4</sub> from LPSCl, resulting in an interphase material with limited local mobility, thus impeding ion transport. Although the addition of Br as a dopant can improve the ionic conductivity of LPSCl by inducing disorder and generating the Li vacancies, it makes the LPSCl more susceptible to PEO and increases the extent of the interfacial reaction. <sup>6</sup>Li–<sup>6</sup>Li EXSY experiments demonstrate spontaneous Li-ion exchange between the PEO and the LPSCl, yet this exchange is significantly hindered by reaction products within the PEO-LPSCl interphase, attributable to their sluggish local dynamics. This study sheds light on the complex interfacial interaction between PEO-LiTFSI and sulfide argyrodite, providing insights into designing solid electrolytes for the new generation of electrochemical devices.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"20 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141871048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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