Jeongha Eom, Yun Seong Cho, Jihun Lee, Jae Won Heo, Iva Plutnarová, Zdeněk Sofer, In Soo Kim, Dongjoon Rhee, Joohoon Kang
Electrochemical water splitting has received tremendous attention as an eco-friendly approach to produce hydrogen. Noble metals and their oxides are commonly used as electrocatalysts to reduce activation energy barriers for hydrogen and oxygen evolution reactions in high-performance electrodes, but their cost, scarcity, and limited stability hinder widespread adoption of electrochemical water splitting. Further advancements are therefore needed to reduce reliance on noble metals and improve the long-term stability. Herein, solution-processed 2D van der Waals (vdW) p–n heterostructures as an interfacial layer between catalysts and the electrode are introduced to enhance the catalytic performance. These heterostructures are formed by sequentially assembling electrochemically exfoliated black phosphorus and molybdenum disulfide nanosheets into electronic-grade p- and n-type semiconductor thin films, with the scalability extending across tens-of-centimeter scale areas. Benefiting from the charge distribution and built-in electric field developed upon heterojunction formation, the vdW heterostructure interfacial layer increases both the catalytic activity and stability of commercial Pt/C and Ir/C catalysts compared to when these catalysts are directly loaded onto electrodes. Additionally, the vdW heterostructure also serves as a template for synthesizing nanostructured Pt and Ir catalysts through electrodeposition, further enhancing the catalytic performance in terms of mass activity and stability.
电化学水分离作为一种生态友好型制氢方法受到了极大关注。贵金属及其氧化物通常用作电催化剂，以降低高性能电极中氢和氧进化反应的活化能障碍，但其成本、稀缺性和有限的稳定性阻碍了电化学分水技术的广泛应用。因此，需要进一步的进步来减少对贵金属的依赖，并提高其长期稳定性。本文引入溶液加工的二维范德华（vdW）p-n 异质结构作为催化剂与电极之间的界面层，以提高催化性能。这些异质结构是通过将电化学剥离的黑磷和二硫化钼纳米片依次组装成电子级 p 型和 n 型半导体薄膜而形成的，其可扩展性可延伸至数十厘米的区域。得益于异质结形成时产生的电荷分布和内置电场，vdW 异质结构界面层提高了商用 Pt/C 和 Ir/C 催化剂的催化活性和稳定性，而不是直接将这些催化剂装载到电极上。此外，vdW 异质结构还可作为通过电沉积合成纳米结构铂和铱催化剂的模板，进一步提高催化活性和稳定性。
{"title":"Scalable 2D Semiconductor-Based van der Waals Heterostructure Interface with Built-in Electric Field for Enhanced Electrochemical Water Splitting","authors":"Jeongha Eom, Yun Seong Cho, Jihun Lee, Jae Won Heo, Iva Plutnarová, Zdeněk Sofer, In Soo Kim, Dongjoon Rhee, Joohoon Kang","doi":"10.1002/sstr.202400257","DOIUrl":"https://doi.org/10.1002/sstr.202400257","url":null,"abstract":"Electrochemical water splitting has received tremendous attention as an eco-friendly approach to produce hydrogen. Noble metals and their oxides are commonly used as electrocatalysts to reduce activation energy barriers for hydrogen and oxygen evolution reactions in high-performance electrodes, but their cost, scarcity, and limited stability hinder widespread adoption of electrochemical water splitting. Further advancements are therefore needed to reduce reliance on noble metals and improve the long-term stability. Herein, solution-processed 2D van der Waals (vdW) p–n heterostructures as an interfacial layer between catalysts and the electrode are introduced to enhance the catalytic performance. These heterostructures are formed by sequentially assembling electrochemically exfoliated black phosphorus and molybdenum disulfide nanosheets into electronic-grade p- and n-type semiconductor thin films, with the scalability extending across tens-of-centimeter scale areas. Benefiting from the charge distribution and built-in electric field developed upon heterojunction formation, the vdW heterostructure interfacial layer increases both the catalytic activity and stability of commercial Pt/C and Ir/C catalysts compared to when these catalysts are directly loaded onto electrodes. Additionally, the vdW heterostructure also serves as a template for synthesizing nanostructured Pt and Ir catalysts through electrodeposition, further enhancing the catalytic performance in terms of mass activity and stability.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"39 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218356","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}
Gwan Hyeon Park, Won-Gwang Lim, Yun Ho Jeong, Song Kyu Kang, Minho Kim, Junhyuk Ji, Jungseub Ha, Sandya Rani Mangishetti, Subin Kim, Yeji Park, Changshin Jo, Won Bae Kim
Electrolyte modification with a high donor-number solvent is necessary to increase sulfur utilization, but it also presents poor compatibility with lithium metal. The amount of the solvent should be optimized to maximize sulfur utilization at the cathode and minimize side reactions with Li metal at the anode. An electrolyte solution comprising 1 vol% N,N-dimethylacetamide (DMA) in a 1,2-dimethoxyethane (DME)/1,3-dioxolane (DOL) co-solvent demonstrated increased discharge capacity and reduced overpotential compared to DME/DOL and DMA/DOL. In addition to electrolyte, modification that creates radical-mediated pathways from a high donor-number solvent, long-cycle performance is achieved by effectively mitigating the shuttling effect and enhancing reaction kinetics with an efficient electrocatalyst. Cobalt doping into TiN introduced an upshift of the d-band center with ferromagnetic properties that suppressed the shuttling effect, activated radical-mediated pathways, and facilitated the Li2S conversion. A multifunctional separator fabricated with N-doped carbon-embedded cobalt-doped titanium nitride nanowires (NC-Ti0.95Co0.05N NWs) under 1 vol% DMA electrolyte achieved a discharge capacity of 464.4 mA h g−1 even after 200 cycles at a decay rate of 0.093% per cycle through the synergistic effects of electrolyte and electrocatalyst modifications. This work highlights the importance of ferromagnetic catalysts with a high donor-number solvent for lithium–sulfur (Li–S) batteries.
为了提高硫的利用率，有必要使用高供体数溶剂对电解质进行改性，但这种溶剂与锂金属的兼容性较差。应优化溶剂的用量，以最大限度地提高硫在阴极的利用率，并尽量减少与锂金属在阳极的副反应。与 DME/DOL 和 DMA/DOL 相比，1vol% N,N-二甲基乙酰胺（DMA）与 1,2-二甲氧基乙烷（DME）/1,3-二氧戊环（DOL）共溶剂的电解质溶液提高了放电容量，降低了过电位。除了对电解质进行改性，从高供体数溶剂中创建以自由基为介导的途径外，还通过有效减轻穿梭效应和利用高效电催化剂增强反应动力学来实现长周期性能。在 TiN 中掺入钴会使具有铁磁性的 d 带中心上移，从而抑制穿梭效应，激活以自由基为媒介的途径，促进 Li2S 的转化。通过电解质和电催化剂改性的协同作用，在 1 vol% DMA 电解质下用掺杂 N 的碳嵌入掺钴氮化钛纳米线（NC-Ti0.95Co0.05N NWs）制造的多功能分离器在 200 个循环后仍能达到 464.4 mA h g-1 的放电容量，衰减率为 0.093%/循环。这项工作凸显了具有高供体数溶剂的铁磁催化剂对锂硫（Li-S）电池的重要性。
{"title":"Activation of the Radical-Mediated Pathway and Facilitation of the Li2S Conversion by N-Doped Carbon-Embedded Ti1–xCoxN Nanowires as a Multifunctional Separator with a High Donor-Number Solvent toward Advanced Lithium–Sulfur Batteries","authors":"Gwan Hyeon Park, Won-Gwang Lim, Yun Ho Jeong, Song Kyu Kang, Minho Kim, Junhyuk Ji, Jungseub Ha, Sandya Rani Mangishetti, Subin Kim, Yeji Park, Changshin Jo, Won Bae Kim","doi":"10.1002/sstr.202400293","DOIUrl":"https://doi.org/10.1002/sstr.202400293","url":null,"abstract":"Electrolyte modification with a high donor-number solvent is necessary to increase sulfur utilization, but it also presents poor compatibility with lithium metal. The amount of the solvent should be optimized to maximize sulfur utilization at the cathode and minimize side reactions with Li metal at the anode. An electrolyte solution comprising 1 vol% <i>N</i>,<i>N</i>-dimethylacetamide (DMA) in a 1,2-dimethoxyethane (DME)/1,3-dioxolane (DOL) co-solvent demonstrated increased discharge capacity and reduced overpotential compared to DME/DOL and DMA/DOL. In addition to electrolyte, modification that creates radical-mediated pathways from a high donor-number solvent, long-cycle performance is achieved by effectively mitigating the shuttling effect and enhancing reaction kinetics with an efficient electrocatalyst. Cobalt doping into TiN introduced an upshift of the d-band center with ferromagnetic properties that suppressed the shuttling effect, activated radical-mediated pathways, and facilitated the Li<sub>2</sub>S conversion. A multifunctional separator fabricated with N-doped carbon-embedded cobalt-doped titanium nitride nanowires (NC-Ti<sub>0.95</sub>Co<sub>0.05</sub>N NWs) under 1 vol% DMA electrolyte achieved a discharge capacity of 464.4 mA h g<sup>−1</sup> even after 200 cycles at a decay rate of 0.093% per cycle through the synergistic effects of electrolyte and electrocatalyst modifications. This work highlights the importance of ferromagnetic catalysts with a high donor-number solvent for lithium–sulfur (Li–S) batteries.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218347","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}
Elham Lori Zoudani, Nam-Trung Nguyen, Navid Kashaninejad
Microneedles hold remarkable potential for providing convenient and unique solutions for disease diagnosis and therapy. However, their integration into clinical practices has been slow, primarily due to the challenge of developing models that meet the criteria of a particular application. A comprehensive and systematic analysis of all aspects of microneedle platforms is imperative to overcome this bottleneck. The analysis involves gathering performance-related information and understanding the factors affecting the functionality of microneedles. The performance of microneedles is heavily influenced by parameters such as dimensions, needle shape, array arrangement, and materials (flexible, stretchable, stimuli-responsive, biodegradable). This article presents a fresh perspective on microneedles, introducing concepts toward optimal designs across various microneedle platforms. This includes application, design, fabrication techniques, and understanding how a specific microneedle design can effectively meet the requirements of a particular application. By addressing these crucial issues, further advancement of microneedle technology occurs.
{"title":"Microneedle Optimization: Toward Enhancing Microneedle's Functionality and Breaking the Traditions","authors":"Elham Lori Zoudani, Nam-Trung Nguyen, Navid Kashaninejad","doi":"10.1002/sstr.202400121","DOIUrl":"https://doi.org/10.1002/sstr.202400121","url":null,"abstract":"Microneedles hold remarkable potential for providing convenient and unique solutions for disease diagnosis and therapy. However, their integration into clinical practices has been slow, primarily due to the challenge of developing models that meet the criteria of a particular application. A comprehensive and systematic analysis of all aspects of microneedle platforms is imperative to overcome this bottleneck. The analysis involves gathering performance-related information and understanding the factors affecting the functionality of microneedles. The performance of microneedles is heavily influenced by parameters such as dimensions, needle shape, array arrangement, and materials (flexible, stretchable, stimuli-responsive, biodegradable). This article presents a fresh perspective on microneedles, introducing concepts toward optimal designs across various microneedle platforms. This includes application, design, fabrication techniques, and understanding how a specific microneedle design can effectively meet the requirements of a particular application. By addressing these crucial issues, further advancement of microneedle technology occurs.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"297 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218335","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}
Jayasmita Jana, Tata Sanjay Kanna Sharma, Beena Mol Babu, Sabah Ansar, Somnath Chowdhury, Balasubramanian Sriram, Sea-Fue Wang, Sung Gu Kang, Jin Suk Chung, Won Mook Choi, Seung Hyun Hur
In this study, a composite comprising a rare-earth metal, samarium vanadate (SmVO4, SmV), anchored to halloysite nanotube (HNT) making SmV/HNT nanocomposite is synthesized for the sensitive electrochemical determination of furaltadone (FLD) through differential pulse voltammetry analysis based on the synergistic effect of SmV/HNT (the catalytic activity and chemical stability of SmV, which was further boosted by the improved surface area and conductance of HNT). Further, in the microscopic studies, it is revealed that SmV exhibits a tetragonal zircon-type crystalline structure, with I41/amd (141) space group, whereas HNT comprises a multiphase kaolin composition as a gibbsite-like octahedral sheet with multivalency, and the morphological irregularities of the individual constituents are rectified in the composite. The SmV/HNT composite is spray-coated on polyethylene terephthalate sheet, which delivered a promising trace level limit of detection (0.009 μm) over a wide working range (0.05–194.4 μm) for FLD. Furthermore, real sample analysis is performed using human serum, and pharmaceutical tablet and the results reveal exceptional repeatability and sensitivity, indicating the real-time application of SmV/HNT in the pharmaceutical domain.
{"title":"Integration of Samarium Vanadate/Halloysite Nanotubes: Electrochemical Determination of Furaltadone Using Flexible Electrode","authors":"Jayasmita Jana, Tata Sanjay Kanna Sharma, Beena Mol Babu, Sabah Ansar, Somnath Chowdhury, Balasubramanian Sriram, Sea-Fue Wang, Sung Gu Kang, Jin Suk Chung, Won Mook Choi, Seung Hyun Hur","doi":"10.1002/sstr.202400287","DOIUrl":"https://doi.org/10.1002/sstr.202400287","url":null,"abstract":"In this study, a composite comprising a rare-earth metal, samarium vanadate (SmVO<sub>4</sub>, SmV), anchored to halloysite nanotube (HNT) making SmV/HNT nanocomposite is synthesized for the sensitive electrochemical determination of furaltadone (FLD) through differential pulse voltammetry analysis based on the synergistic effect of SmV/HNT (the catalytic activity and chemical stability of SmV, which was further boosted by the improved surface area and conductance of HNT). Further, in the microscopic studies, it is revealed that SmV exhibits a tetragonal zircon-type crystalline structure, with I4<sub>1</sub>/<i>amd</i> (141) space group, whereas HNT comprises a multiphase kaolin composition as a gibbsite-like octahedral sheet with multivalency, and the morphological irregularities of the individual constituents are rectified in the composite. The SmV/HNT composite is spray-coated on polyethylene terephthalate sheet, which delivered a promising trace level limit of detection (0.009 μ<span>m</span>) over a wide working range (0.05–194.4 μ<span>m</span>) for FLD. Furthermore, real sample analysis is performed using human serum, and pharmaceutical tablet and the results reveal exceptional repeatability and sensitivity, indicating the real-time application of SmV/HNT in the pharmaceutical domain.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"75 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218346","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}
Expansion microscopy (ExM) has gained increasing popularity for 3D ultrastructural imaging of cultured cells and tissue slices at nanoscale resolution using conventional microscopes via physical expansion of biological tissues. However, its application to collagen-abundant thick tissues is still challenging. Herein, a new method, collagen ExM (ColExM), optimized for expanding tissues containing more than 70% collagen, is demonstrated. ColExM succeeds in 4.5-fold linear expansion with minimal structural distortion of corneal and skin tissues. It is compatible with immunostaining, allowing super-resolution visualization of 3D neural structures innervating hair follicles, corneas, and pancreatic tumors with high stromal collagen content. The method succeeds in identifying individual mitochondria and previously unrecognized dendritic spinelike structures of corneal nerves. It also enables fine mapping of structural rearrangement of tight junctions and actin cytoskeletons. Therefore, ColExM can facilitate the exploration of 3D nanoscale structures in collagen-rich tissues.
{"title":"Super-Resolution Imaging in Collagen-Abundant Thick Tissues","authors":"Ya-Han Chuang, Yueh-Feng Wu, Ya-Hui Lin, Yin-Hsu Chen, Yu-Xian Zhou, Shao-Chun Hsu, Hsin-Mei Lee, Ann-Shyn Chiang, Yunching Chen, Shiang-Jiuun Chen, Sung-Jan Lin, Li-An Chu","doi":"10.1002/sstr.202400231","DOIUrl":"https://doi.org/10.1002/sstr.202400231","url":null,"abstract":"Expansion microscopy (ExM) has gained increasing popularity for 3D ultrastructural imaging of cultured cells and tissue slices at nanoscale resolution using conventional microscopes via physical expansion of biological tissues. However, its application to collagen-abundant thick tissues is still challenging. Herein, a new method, collagen ExM (ColExM), optimized for expanding tissues containing more than 70% collagen, is demonstrated. ColExM succeeds in 4.5-fold linear expansion with minimal structural distortion of corneal and skin tissues. It is compatible with immunostaining, allowing super-resolution visualization of 3D neural structures innervating hair follicles, corneas, and pancreatic tumors with high stromal collagen content. The method succeeds in identifying individual mitochondria and previously unrecognized dendritic spinelike structures of corneal nerves. It also enables fine mapping of structural rearrangement of tight junctions and actin cytoskeletons. Therefore, ColExM can facilitate the exploration of 3D nanoscale structures in collagen-rich tissues.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"27 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142218348","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}
Jae Ho Kim, Geonguk Kim, Sung-Jo Kim, Yu Bhin Kim, Jae-Wook Kang, Jin Woo Choi, Jin-Woo Oh, Myungkwan Song
Flexible Organic Light-Emitting Diodes
柔性有机发光二极管
{"title":"Novel Strategy towards Efficiency Enhancement of Flexible Optoelectronic Devices with Engineered M13 Bacteriophage","authors":"Jae Ho Kim, Geonguk Kim, Sung-Jo Kim, Yu Bhin Kim, Jae-Wook Kang, Jin Woo Choi, Jin-Woo Oh, Myungkwan Song","doi":"10.1002/sstr.202470036","DOIUrl":"https://doi.org/10.1002/sstr.202470036","url":null,"abstract":"<b>Flexible Organic Light-Emitting Diodes</b>","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"77 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141935916","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}
Nickel oxide (NiOx) serves as one of the most promising hole transport materials for perovskite light‐emitting diodes (PeLEDs). However, only moderate PeLED performances have been reported on the pristine NiOx layer due to insufficient hole injection, interfacial exciton quenching, and poor perovskite quality. Herein, a multifunctional molecule of 3‐mercapto‐1‐propanesulfonate (MPS) is demonstrated to successfully tailor the NiOx–perovskite heterogenous interface by addressing the above issues. In detail, the large binding energy between mercapto sulfur and nickel induces preferential self‐assembly of the mercapto group on the NiOx surface, which simultaneously enlarges the NiOx work function by the formation of interfacial dipole and suppresses the trap‐assisted exciton quenching by the passivation of the oxygen vacancies. Meanwhile, the self‐assembled MPS on NiOx also favors high‐quality perovskite films with good morphology, high crystallinity, and reduced defects for efficient carrier radiative recombination. As a result, blue PeLEDs show a remarkable efficiency of 10.4%, representing one of the highest efficiencies for NiOx‐based blue PeLEDs, as well as a very low turn‐on voltage of 2.8 V. Consequently, this work contributes to an efficient approach to tailor the NiOx–perovskite interface for highly efficient blue PeLEDs.
{"title":"Tailoring Niox/Perovskite Interface via a Multifunctional Self‐Assembled Molecule for High‐Performance Blue Perovskite Light‐Emitting Diodes","authors":"Huifeng Ji, Zhenwei Ren, Ran Chen, Chengzhao Luo, Xin Zhou, Zhiyong Zheng, Hengfei Shi, Yuze Zhang, Hua Chen, Huanxi Peng, Yu Chen","doi":"10.1002/sstr.202400153","DOIUrl":"https://doi.org/10.1002/sstr.202400153","url":null,"abstract":"\u0000Nickel oxide (NiOx) serves as one of the most promising hole transport materials for perovskite light‐emitting diodes (PeLEDs). However, only moderate PeLED performances have been reported on the pristine NiOx layer due to insufficient hole injection, interfacial exciton quenching, and poor perovskite quality. Herein, a multifunctional molecule of 3‐mercapto‐1‐propanesulfonate (MPS) is demonstrated to successfully tailor the NiOx–perovskite heterogenous interface by addressing the above issues. In detail, the large binding energy between mercapto sulfur and nickel induces preferential self‐assembly of the mercapto group on the NiOx surface, which simultaneously enlarges the NiOx work function by the formation of interfacial dipole and suppresses the trap‐assisted exciton quenching by the passivation of the oxygen vacancies. Meanwhile, the self‐assembled MPS on NiOx also favors high‐quality perovskite films with good morphology, high crystallinity, and reduced defects for efficient carrier radiative recombination. As a result, blue PeLEDs show a remarkable efficiency of 10.4%, representing one of the highest efficiencies for NiOx‐based blue PeLEDs, as well as a very low turn‐on voltage of 2.8 V. Consequently, this work contributes to an efficient approach to tailor the NiOx–perovskite interface for highly efficient blue PeLEDs.","PeriodicalId":21841,"journal":{"name":"Small Structures","volume":"62 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141926875","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}
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}
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