Qi Wang, Guihui Yu, Bi Luo, Weijie Ji, Zihang Liu, Minghuang Li, Yutong Nong, Yi Tian, Xiaowei Wang, Jiafeng Zhang, Chi-Liang Chen, Chung-Kai Chang, Zhiyuan Sang, Zaowen Zhao, Ruirui Zhao, Ji Liang
Advancing the high-voltage stability of the O3-type layered cathodes for sodium-ion batteries is critical to boost their progress in energy storage applications. However, this type of cathode often suffers from intricate phase transition and structural degradation at high voltages (i.e., >4.0 V vs Na+/Na), resulting in rapid capacity decay. Here, we present a Li/Ti cosubstitution strategy to modify the electronic configuration of oxygen elements in the O3-type layered oxide cathode. This deliberate modulation simultaneously mitigates the phase transitions and counteracts the weakening of the shielding effect resulting from the extraction of sodium ions, thus enhancing the electrostatic bonding within the TM layer and inducing and optimizing the O3-OP2 phase transition occurring in the voltage range of 2.0-4.3 V. Consequently, the cosubstituted NaLi1/9Ni1/3Mn4/9Ti1/9O2 exhibits an astounding capacity of 161.2 mAh g-1 in the voltage range of 2.0-4.3 V at 1C, and stable cycling up to 100 cycles has been achieved. This work shows the impact mechanism of element substitution on interlayer forces and phase transitions, providing a crucial reference for the optimization of O3-type materials.
提高钠离子电池 O3 型层状阴极的高压稳定性对于促进其在储能应用领域的发展至关重要。然而,这种类型的阴极在高电压下(即对 Na+/Na >4.0 V)往往会出现错综复杂的相变和结构退化,从而导致容量快速衰减。在此,我们提出了一种锂/钛共置换策略,以改变 O3 型层状氧化物阴极中氧元素的电子构型。这种有意的调制同时缓解了相变,并抵消了钠离子萃取导致的屏蔽效应的减弱,从而增强了 TM 层内的静电结合,诱导并优化了发生在 2.0-4.3 V 电压范围内的 O3-OP2 相变。因此,共取代 NaLi1/9Ni1/3Mn4/9Ti1/9O2 在 2.0-4.3 V 的电压范围内于 1C 时显示出 161.2 mAh g-1 的惊人容量,并实现了长达 100 次的稳定循环。这项研究显示了元素替代对层间作用力和相变的影响机制,为优化 O3 型材料提供了重要参考。
{"title":"Suppression of Adverse Phase Transition of Layered Oxide Cathode via Local Electronic Structure Regulation for High-Capacity Sodium-Ion Batteries.","authors":"Qi Wang, Guihui Yu, Bi Luo, Weijie Ji, Zihang Liu, Minghuang Li, Yutong Nong, Yi Tian, Xiaowei Wang, Jiafeng Zhang, Chi-Liang Chen, Chung-Kai Chang, Zhiyuan Sang, Zaowen Zhao, Ruirui Zhao, Ji Liang","doi":"10.1021/acsnano.4c04847","DOIUrl":"https://doi.org/10.1021/acsnano.4c04847","url":null,"abstract":"<p><p>Advancing the high-voltage stability of the O3-type layered cathodes for sodium-ion batteries is critical to boost their progress in energy storage applications. However, this type of cathode often suffers from intricate phase transition and structural degradation at high voltages (i.e., >4.0 V vs Na<sup>+</sup>/Na), resulting in rapid capacity decay. Here, we present a Li/Ti cosubstitution strategy to modify the electronic configuration of oxygen elements in the O3-type layered oxide cathode. This deliberate modulation simultaneously mitigates the phase transitions and counteracts the weakening of the shielding effect resulting from the extraction of sodium ions, thus enhancing the electrostatic bonding within the TM layer and inducing and optimizing the O3-OP2 phase transition occurring in the voltage range of 2.0-4.3 V. Consequently, the cosubstituted NaLi<sub>1/9</sub>Ni<sub>1/3</sub>Mn<sub>4/9</sub>Ti<sub>1/9</sub>O<sub>2</sub> exhibits an astounding capacity of 161.2 mAh g<sup>-1</sup> in the voltage range of 2.0-4.3 V at 1C, and stable cycling up to 100 cycles has been achieved. This work shows the impact mechanism of element substitution on interlayer forces and phase transitions, providing a crucial reference for the optimization of O3-type materials.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464230","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chung Won Lee, Changhyeon Yoo, Sang Sub Han, Yu-Jin Song, Seung Ju Kim, Jung Han Kim, Yeonwoong Jung
Prevailing over the bottleneck of von Neumann computing has been significant attention due to the inevitableness of proceeding through enormous data volumes in current digital technologies. Inspired by the human brain's operational principle, the artificial synapse of neuromorphic computing has been explored as an emerging solution. Especially, the optoelectronic synapse is of growing interest as vision is an essential source of information in which dealing with optical stimuli is vital. Herein, flexible optoelectronic synaptic devices composed of centimeter-scale tellurium dioxide (TeO2) films detecting and exhibiting synaptic characteristics to broadband wavelengths are presented. The TeO2-based flexible devices demonstrate a comprehensive set of emulating basic optoelectronic synaptic characteristics; i.e., excitatory postsynaptic current (EPSC), paired-pulse facilitation (PPF), conversion of short-term to long-term memory, and learning/forgetting. Furthermore, they feature linear and symmetric conductance synaptic weight updates at various wavelengths, which are applicable to broadband neuromorphic computations. Based on this large set of synaptic attributes, a variety of applications such as logistic functions or deep learning and image recognition as well as learning simulations are demonstrated. This work proposes a significant milestone of wafer-scale metal oxide semiconductor-based artificial synapses solely utilizing their optoelectronic features and mechanical flexibility, which is attractive toward scaled-up neuromorphic architectures.
{"title":"Centimeter-Scale Tellurium Oxide Films for Artificial Optoelectronic Synapses with Broadband Responsiveness and Mechanical Flexibility.","authors":"Chung Won Lee, Changhyeon Yoo, Sang Sub Han, Yu-Jin Song, Seung Ju Kim, Jung Han Kim, Yeonwoong Jung","doi":"10.1021/acsnano.4c04851","DOIUrl":"https://doi.org/10.1021/acsnano.4c04851","url":null,"abstract":"<p><p>Prevailing over the bottleneck of von Neumann computing has been significant attention due to the inevitableness of proceeding through enormous data volumes in current digital technologies. Inspired by the human brain's operational principle, the artificial synapse of neuromorphic computing has been explored as an emerging solution. Especially, the optoelectronic synapse is of growing interest as vision is an essential source of information in which dealing with optical stimuli is vital. Herein, flexible optoelectronic synaptic devices composed of centimeter-scale tellurium dioxide (TeO<sub>2</sub>) films detecting and exhibiting synaptic characteristics to broadband wavelengths are presented. The TeO<sub>2</sub>-based flexible devices demonstrate a comprehensive set of emulating basic optoelectronic synaptic characteristics; i.e., excitatory postsynaptic current (EPSC), paired-pulse facilitation (PPF), conversion of short-term to long-term memory, and learning/forgetting. Furthermore, they feature linear and symmetric conductance synaptic weight updates at various wavelengths, which are applicable to broadband neuromorphic computations. Based on this large set of synaptic attributes, a variety of applications such as logistic functions or deep learning and image recognition as well as learning simulations are demonstrated. This work proposes a significant milestone of wafer-scale metal oxide semiconductor-based artificial synapses solely utilizing their optoelectronic features and mechanical flexibility, which is attractive toward scaled-up neuromorphic architectures.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jing Xu, Pingan Han, Yang Jin, Hongfei Lu, Bing Sun, Beibei Gao, Tingting He, Xiaoxue Xu, Nicola Pinna, Guoxiu Wang
The side reactions and dendrite growth at the interface of Zn anodes greatly limit their practical applications in Zn metal batteries. Herein, we propose a hybrid molecular sieve-based interfacial layer (denoted as Z7M3) with a hierarchical porous structure for Zn metal anodes, which contains 70 vol % microporous ZSM-5 molecular sieves and 30 vol % mesoporous MCM-41 molecular sieves. Through comprehensive molecular dynamics simulations, we demonstrate that the mesopores (∼2.5 nm) of MCM-41 can limit the disordered diffusion of free water molecules and increase the wettability of the interfacial layer toward aqueous electrolytes. In addition, the micropores (∼0.56 nm) of ZSM-5 can optimize the Zn2+ solvation structures by reducing the bonded water molecules, which simultaneously decrease the constraint force of solvated water molecules to Zn2+ ions, thus promoting the penetrability and diffusion kinetics of Zn2+ ions in Z7M3. The synergetic effects from the hybrid molecular sieves maintain a constant Zn2+ concentration on the surface of the Zn electrode during Zn deposition, contributing to dendrite-free Zn anodes. Consequently, Z7M3-coated Zn electrodes achieved excellent cycling stability in both half and full cells.
{"title":"Hybrid Molecular Sieve-Based Interfacial Layer with Physical Confinement and Desolvation Effect for Dendrite-free Zinc Metal Anodes.","authors":"Jing Xu, Pingan Han, Yang Jin, Hongfei Lu, Bing Sun, Beibei Gao, Tingting He, Xiaoxue Xu, Nicola Pinna, Guoxiu Wang","doi":"10.1021/acsnano.4c04632","DOIUrl":"https://doi.org/10.1021/acsnano.4c04632","url":null,"abstract":"<p><p>The side reactions and dendrite growth at the interface of Zn anodes greatly limit their practical applications in Zn metal batteries. Herein, we propose a hybrid molecular sieve-based interfacial layer (denoted as Z<sub>7</sub>M<sub>3</sub>) with a hierarchical porous structure for Zn metal anodes, which contains 70 vol % microporous ZSM-5 molecular sieves and 30 vol % mesoporous MCM-41 molecular sieves. Through comprehensive molecular dynamics simulations, we demonstrate that the mesopores (∼2.5 nm) of MCM-41 can limit the disordered diffusion of free water molecules and increase the wettability of the interfacial layer toward aqueous electrolytes. In addition, the micropores (∼0.56 nm) of ZSM-5 can optimize the Zn<sup>2+</sup> solvation structures by reducing the bonded water molecules, which simultaneously decrease the constraint force of solvated water molecules to Zn<sup>2+</sup> ions, thus promoting the penetrability and diffusion kinetics of Zn<sup>2+</sup> ions in Z<sub>7</sub>M<sub>3</sub>. The synergetic effects from the hybrid molecular sieves maintain a constant Zn<sup>2+</sup> concentration on the surface of the Zn electrode during Zn deposition, contributing to dendrite-free Zn anodes. Consequently, Z<sub>7</sub>M<sub>3</sub>-coated Zn electrodes achieved excellent cycling stability in both half and full cells.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Heping Shang, Chunyang Li, Zeyu Cai, Yi Hao, Yini Cao, Weili Jia, Lanfang Han, Jason C White, Chuanxin Ma, Baoshan Xing
Nanotechnology has demonstrated significant potential to improve agricultural production and increase crop tolerance to abiotic stress including exposure to heavy metals. The present study investigated the mechanisms by which aloe vera extract gel-biosynthesized (AVGE) selenium nanoparticles (Se NPs) alleviated cadmium (Cd)-induced toxicity to rice (Oryza sativa L.). AVGE Se NPs, chemically synthesized bare Se NPs, and NaSeO3 as an ionic control were applied to Cd-stressed rice seedlings via root exposure in both hydroponic and soil systems. Upon exposure to AVGE Se NPs at 15 mg Se/L, the fresh root biomass was significantly increased by 100.7% and 19.5% as compared to Cd control and conventional bare Se NPs. Transcriptional analyses highlighted that AVGE Se NPs activated stress signaling and defense related pathways, including glutathione metabolism, phenylpropanoid biosynthesis and plant hormone signal transduction. Specifically, exposure to AVGE Se NPs upregulated the expression of genes associated with the gibberellic acid (GA) biosynthesis by and 4.79- and 3.29-fold as compared to the Cd-alone treatment and the untreated control, respectively. Importantly, AVGE Se NPs restored the composition of the endophyte community and recruit of beneficial species under Cd exposure; the relative abundance of Azospirillum was significantly increased in roots, shoots, and the rhizosphere soil by 0.73-, 4.58- and 0.37-fold, respectively, relative to the Cd-alone treatment. Collectively, these findings highlight the significant potential of AVGE Se NPs to enhance plant growth and to minimize the Cd-induced toxicity in rice and provide a promising nanoenabled strategy to enhance food safety upon crop cultivation in contaminated agricultural soils.
纳米技术在改善农业生产和提高作物对非生物胁迫(包括重金属暴露)的耐受性方面具有巨大潜力。本研究调查了芦荟提取物凝胶生物合成(AVGE)硒纳米粒子(Se NPs)减轻镉(Cd)诱导的水稻(Oryza sativa L.)毒性的机制。在水培和土壤系统中,将 AVGE Se NPs、化学合成的裸 Se NPs 和 NaSeO3 作为离子对照,通过根暴露施用于受 Cd 胁迫的水稻秧苗。与镉对照和传统裸Se NPs相比,暴露于15 mg Se/L的AVGE Se NPs后,新鲜根生物量分别显著增加了100.7%和19.5%。转录分析表明,AVGE Se NPs 激活了与胁迫信号和防御相关的通路,包括谷胱甘肽代谢、苯丙类生物合成和植物激素信号转导。具体来说,与单用 Cd 处理和未处理对照相比,暴露于 AVGE Se NPs 会上调赤霉素(GA)生物合成相关基因的表达,分别为 4.79 倍和 3.29 倍。重要的是,在镉暴露条件下,AVGE Se NPs 恢复了内生菌群落的组成并招募了有益物种;与单镉处理相比,根、芽和根瘤土壤中 Azospirillum 的相对丰度分别显著增加了 0.73 倍、4.58 倍和 0.37 倍。总之,这些研究结果凸显了 AVGE Se NPs 在促进植物生长和最大程度降低镉诱导的水稻毒性方面的巨大潜力,并为在受污染的农业土壤中种植作物时提高食品安全提供了一种前景广阔的纳米策略。
{"title":"Biosynthesized Selenium Nanoparticles as an Effective Tool to Combat Soil Metal Stresses in Rice (<i>Oryza sativa</i> L.).","authors":"Heping Shang, Chunyang Li, Zeyu Cai, Yi Hao, Yini Cao, Weili Jia, Lanfang Han, Jason C White, Chuanxin Ma, Baoshan Xing","doi":"10.1021/acsnano.4c04215","DOIUrl":"https://doi.org/10.1021/acsnano.4c04215","url":null,"abstract":"<p><p>Nanotechnology has demonstrated significant potential to improve agricultural production and increase crop tolerance to abiotic stress including exposure to heavy metals. The present study investigated the mechanisms by which aloe vera extract gel-biosynthesized (AVGE) selenium nanoparticles (Se NPs) alleviated cadmium (Cd)-induced toxicity to rice (<i>Oryza sativa</i> L.). AVGE Se NPs, chemically synthesized bare Se NPs, and NaSeO<sub>3</sub> as an ionic control were applied to Cd-stressed rice seedlings via root exposure in both hydroponic and soil systems. Upon exposure to AVGE Se NPs at 15 mg Se/L, the fresh root biomass was significantly increased by 100.7% and 19.5% as compared to Cd control and conventional bare Se NPs. Transcriptional analyses highlighted that AVGE Se NPs activated stress signaling and defense related pathways, including glutathione metabolism, phenylpropanoid biosynthesis and plant hormone signal transduction. Specifically, exposure to AVGE Se NPs upregulated the expression of genes associated with the gibberellic acid (GA) biosynthesis by and 4.79- and 3.29-fold as compared to the Cd-alone treatment and the untreated control, respectively. Importantly, AVGE Se NPs restored the composition of the endophyte community and recruit of beneficial species under Cd exposure; the relative abundance of <i>Azospirillum</i> was significantly increased in roots, shoots, and the rhizosphere soil by 0.73-, 4.58- and 0.37-fold, respectively, relative to the Cd-alone treatment. Collectively, these findings highlight the significant potential of AVGE Se NPs to enhance plant growth and to minimize the Cd-induced toxicity in rice and provide a promising nanoenabled strategy to enhance food safety upon crop cultivation in contaminated agricultural soils.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475360","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tianhao Ding, Yang Wang, Yanchun Meng, Ercan Wu, Qianwen Shao, Shiqi Lin, Yifei Yu, Jun Qian, Qin He, Jian Zhang, Jing Wang, Daniel S Kohane, Changyou Zhan
Liposomes are versatile drug delivery systems in clinical use for cancer and many other diseases. Unfortunately, PEGylated liposomal doxorubicin (sLip/DOX) exhibits serious dose-limiting cutaneous toxicities, which are closely related to the extravascular accumulation of sLip/DOX in the dermis. No clinical interventions have been proposed for cutaneous toxicities due to the elusive transport pathways. Herein, we showed that the reciprocal interaction between liposomes and neutrophils played pivotal roles in liposome extravasation into the dermis. Neutrophils captured liposomes via the complement receptor 3 (CD11b/CD18) recognizing the fragment of complement component C3 (iC3b) deposited on the liposomal surface. Uptake of liposomes also activated neutrophils to induce CD11b upregulation and enhanced the ability of neutrophils to migrate outside the capillaries. Furthermore, inhibition of complement activation either by CRIg-L-FH (a C3b/iC3b targeted complement inhibitor) or blocking the phosphate negative charge in mPEG-DSPE could significantly reduce liposome uptake by neutrophils and alleviate the cutaneous accumulation of liposomes. These results validated the liposome extravasation pathway mediated by neutrophils and provided potential solutions to the devastating cutaneous toxicities occurring during sLip/DOX treatment.
{"title":"Reciprocal Interaction with Neutrophils Facilitates Cutaneous Accumulation of Liposomes.","authors":"Tianhao Ding, Yang Wang, Yanchun Meng, Ercan Wu, Qianwen Shao, Shiqi Lin, Yifei Yu, Jun Qian, Qin He, Jian Zhang, Jing Wang, Daniel S Kohane, Changyou Zhan","doi":"10.1021/acsnano.4c06638","DOIUrl":"https://doi.org/10.1021/acsnano.4c06638","url":null,"abstract":"<p><p>Liposomes are versatile drug delivery systems in clinical use for cancer and many other diseases. Unfortunately, PEGylated liposomal doxorubicin (sLip/DOX) exhibits serious dose-limiting cutaneous toxicities, which are closely related to the extravascular accumulation of sLip/DOX in the dermis. No clinical interventions have been proposed for cutaneous toxicities due to the elusive transport pathways. Herein, we showed that the reciprocal interaction between liposomes and neutrophils played pivotal roles in liposome extravasation into the dermis. Neutrophils captured liposomes via the complement receptor 3 (CD11b/CD18) recognizing the fragment of complement component C3 (iC3b) deposited on the liposomal surface. Uptake of liposomes also activated neutrophils to induce CD11b upregulation and enhanced the ability of neutrophils to migrate outside the capillaries. Furthermore, inhibition of complement activation either by CRIg-L-FH (a C3b/iC3b targeted complement inhibitor) or blocking the phosphate negative charge in mPEG-DSPE could significantly reduce liposome uptake by neutrophils and alleviate the cutaneous accumulation of liposomes. These results validated the liposome extravasation pathway mediated by neutrophils and provided potential solutions to the devastating cutaneous toxicities occurring during sLip/DOX treatment.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Separating xylene isomers is a challenging task due to their similar physical and chemical properties. In this study, we developed a molecular sieve incorporating a reduced graphene oxide (rGO) membrane for the precise differentiation of xylene isomers. We fabricated GO membranes using a vacuum filtration technique followed by thermal-induced reduction to produce rGO membranes with precisely controllable interlayer spacing. Notably, we could finely tune the interlayer spacing of the rGO membrane from 8.0 to 5.0 Å by simply varying the thermal reduction temperature. We investigated the reverse osmosis separation ability of the rGO membranes for xylene isomers and found that the rGO membrane with an interlayer spacing of 6.1 Å showed a high single component permeance of 0.17 and 0.04 L m-2 h-1 bar-1 for para- and ortho-xylene, respectively, exhibiting clear permselectivity. The separation factor reached 3.4 and 2.8 when 90:10 and 50:50 feed mixtures were used, respectively, with permeance 1 order of magnitude higher than that of current state-of-the-art reverse osmosis membranes. Additionally, the membrane showed negligible permeance and selectivity decay even after continuous operation for more than 5 days, suggesting commendable membrane resistance to solvent swelling and operating pressure.
{"title":"Discrimination of Xylene Isomers by Precisely Tuning the Interlayer Spacing of Reduced Graphene Oxide Membrane.","authors":"Haftu Gebrekiros Alemayehu, Junjun Hou, Adeel Ahmad Qureshi, Yongji Yao, Zhifei Sun, Mingzheng Yan, Congying Wang, Luqi Liu, Zhiyong Tang, Lianshan Li","doi":"10.1021/acsnano.4c05461","DOIUrl":"https://doi.org/10.1021/acsnano.4c05461","url":null,"abstract":"<p><p>Separating xylene isomers is a challenging task due to their similar physical and chemical properties. In this study, we developed a molecular sieve incorporating a reduced graphene oxide (rGO) membrane for the precise differentiation of xylene isomers. We fabricated GO membranes using a vacuum filtration technique followed by thermal-induced reduction to produce rGO membranes with precisely controllable interlayer spacing. Notably, we could finely tune the interlayer spacing of the rGO membrane from 8.0 to 5.0 Å by simply varying the thermal reduction temperature. We investigated the reverse osmosis separation ability of the rGO membranes for xylene isomers and found that the rGO membrane with an interlayer spacing of 6.1 Å showed a high single component permeance of 0.17 and 0.04 L m<sup>-2</sup> h<sup>-1</sup> bar<sup>-1</sup> for <i>para-</i> and <i>ortho</i>-xylene, respectively, exhibiting clear permselectivity. The separation factor reached 3.4 and 2.8 when 90:10 and 50:50 feed mixtures were used, respectively, with permeance 1 order of magnitude higher than that of current state-of-the-art reverse osmosis membranes. Additionally, the membrane showed negligible permeance and selectivity decay even after continuous operation for more than 5 days, suggesting commendable membrane resistance to solvent swelling and operating pressure.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Athulya K Muraleedharan, Kevin Co, Maxime Vallet, Abdelali Zaki, Fabienne Karolak, Christine Bogicevic, Karen Perronet, Brahim Dkhil, Charles Paillard, Céline Fiorini-Debuisschert, François Treussart
Ferroelectric materials display exotic polarization textures at the nanoscale that could be used to improve the energetic efficiency of electronic components. The vast majority of studies were conducted in two dimensions on thin films that can be further nanostructured, but very few studies address the situation of individual isolated nanocrystals (NCs) synthesized in solution, while such structures could have other fields of applications. In this work, we experimentally and theoretically studied the polarization texture of ferroelectric barium titanate (BaTiO3, BTO) NCs attached to a conductive substrate and surrounded by air. We synthesized NCs of well-defined quasicubic shape and 160 nm average size that conserve the tetragonal structure of BTO at room temperature. We then investigated the inverse piezoelectric properties of such pristine individual NCs by vector piezoresponse force microscopy (PFM), taking particular care to suppress electrostatic artifacts. In all of the NCs studied, we could not detect any vertical PFM signal, and the maps of the lateral response all displayed larger displacement amplitude on the edges with deformations converging toward the center. Using field phase simulations dedicated to ferroelectric nanostructures, we were able to predict the equilibrium polarization texture. These simulations revealed that the NC core is composed of 180° up and down domains defining the polar axis that rotate by 90° in the two facets orthogonal to this axis, eventually lying within these planes forming a layer of about 10 nm thickness mainly composed of 180° domains along an edge. From this polarization distribution, we predicted the lateral PFM response, which was revealed to be in very good qualitative agreement with the experimental observations. This work positions PFM as a relevant tool to evaluate the potential of complex ferroelectric nanostructures to be used as sensors.
{"title":"Ferroelectric Texture of Individual Barium Titanate Nanocrystals.","authors":"Athulya K Muraleedharan, Kevin Co, Maxime Vallet, Abdelali Zaki, Fabienne Karolak, Christine Bogicevic, Karen Perronet, Brahim Dkhil, Charles Paillard, Céline Fiorini-Debuisschert, François Treussart","doi":"10.1021/acsnano.4c02291","DOIUrl":"https://doi.org/10.1021/acsnano.4c02291","url":null,"abstract":"<p><p>Ferroelectric materials display exotic polarization textures at the nanoscale that could be used to improve the energetic efficiency of electronic components. The vast majority of studies were conducted in two dimensions on thin films that can be further nanostructured, but very few studies address the situation of individual isolated nanocrystals (NCs) synthesized in solution, while such structures could have other fields of applications. In this work, we experimentally and theoretically studied the polarization texture of ferroelectric barium titanate (BaTiO<sub>3</sub>, BTO) NCs attached to a conductive substrate and surrounded by air. We synthesized NCs of well-defined quasicubic shape and 160 nm average size that conserve the tetragonal structure of BTO at room temperature. We then investigated the inverse piezoelectric properties of such pristine individual NCs by vector piezoresponse force microscopy (PFM), taking particular care to suppress electrostatic artifacts. In all of the NCs studied, we could not detect any vertical PFM signal, and the maps of the lateral response all displayed larger displacement amplitude on the edges with deformations converging toward the center. Using field phase simulations dedicated to ferroelectric nanostructures, we were able to predict the equilibrium polarization texture. These simulations revealed that the NC core is composed of 180° up and down domains defining the polar axis that rotate by 90° in the two facets orthogonal to this axis, eventually lying within these planes forming a layer of about 10 nm thickness mainly composed of 180° domains along an edge. From this polarization distribution, we predicted the lateral PFM response, which was revealed to be in very good qualitative agreement with the experimental observations. This work positions PFM as a relevant tool to evaluate the potential of complex ferroelectric nanostructures to be used as sensors.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Continuous rotation of a fragile, photosensitive microrod in a safe, flexible way remains challenging in spite of its importance to microelectro-mechanical systems. We propose a photovoltaic strategy to continuously rotate a fragile, fluorescent microrod on a LiNbO3/Fe (LN/Fe) substrate using a continuous wave visible (473 nm) laser beam with an ultralow power (few tens of μW) and a simple structure (Gaussian profile). This strategy does not require the laser spot to cover the entire microrod nor does it result in a sharp temperature rise on the microrod. Both experiments and simulation reveal that the strongest photovoltaic field generated beside the laser spot firmly traps one corner of the microrod and the axisymmetric photovoltaic field exerts an electrostatic torque on the microrod driving it to rotate continuously around the laser spot. The dependence of the rotation rate on the laser power indicates contributions from both deep and shallow photovoltaic centers. This rotation mode, combined with the transportation mode, enables the controllable movement of an individual microrod along any complex trajectory with any specific orientation. The tuning of the end-emitting spectrum and the photothermal cutting of the fluorescent microrod are also realized by properly configuring the laser illumination. By taking a microrod as the emitter and a polystyrene microsphere as the focusing lens, we demonstrate the photovoltaic assembly of a microscale light-source system with both spectrum and divergence-angle tunabilities, which are realized by adjusting the photoexcitation position along the microrod and the geometry relationship in the system, respectively.
{"title":"Photovoltaic Rotation and Transportation of a Fragile Fluorescent Microrod Toward Assembling a Tunable Light-Source System.","authors":"Jinghui Yan, Zuoxuan Gao, Lihong Shi, Mengtong Wang, Xiaohu Liu, Chenyu Li, Zechao Huai, Cheng Wang, Lina Zhang, Xuan Wang, Wenbo Yan","doi":"10.1021/acsnano.4c06418","DOIUrl":"https://doi.org/10.1021/acsnano.4c06418","url":null,"abstract":"<p><p>Continuous rotation of a fragile, photosensitive microrod in a safe, flexible way remains challenging in spite of its importance to microelectro-mechanical systems. We propose a photovoltaic strategy to continuously rotate a fragile, fluorescent microrod on a LiNbO<sub>3</sub>/Fe (LN/Fe) substrate using a continuous wave visible (473 nm) laser beam with an ultralow power (few tens of μW) and a simple structure (Gaussian profile). This strategy does not require the laser spot to cover the entire microrod nor does it result in a sharp temperature rise on the microrod. Both experiments and simulation reveal that the strongest photovoltaic field generated beside the laser spot firmly traps one corner of the microrod and the axisymmetric photovoltaic field exerts an electrostatic torque on the microrod driving it to rotate continuously around the laser spot. The dependence of the rotation rate on the laser power indicates contributions from both deep and shallow photovoltaic centers. This rotation mode, combined with the transportation mode, enables the controllable movement of an individual microrod along any complex trajectory with any specific orientation. The tuning of the end-emitting spectrum and the photothermal cutting of the fluorescent microrod are also realized by properly configuring the laser illumination. By taking a microrod as the emitter and a polystyrene microsphere as the focusing lens, we demonstrate the photovoltaic assembly of a microscale light-source system with both spectrum and divergence-angle tunabilities, which are realized by adjusting the photoexcitation position along the microrod and the geometry relationship in the system, respectively.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475374","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Global warming is a crisis that humanity must face together. With greenhouse gases (GHGs) as the main factor causing global warming, the adoption of relevant processes to eliminate them is essential. With the advantages of high specific surface area, large pore volume, and tunable synthesis, metal-organic frameworks (MOFs) have attracted much attention in GHG storage, adsorption, separation, and catalysis. However, as the pool of MOFs expands rapidly with new syntheses and discoveries, finding a suitable MOF for a particular application is highly challenging. In this regard, high-throughput computational screening is considered the most effective research method for screening a large number of materials to discover high-performance target MOFs. Typically, high-throughput computational screening generates voluminous and multidimensional data, which is well suited for machine learning (ML) training to improve the screening efficiency and explore the relationships between the multidimensional data in depth. This Review summarizes the general process and common methods for using ML to screen MOFs in the field of GHG removal. It also addresses the challenges faced by ML in exploring the MOF space and potential directions for the future development of ML for MOF screening. This aims to enhance the understanding of the integration of ML and MOFs in various fields and broaden the application and development ideas of MOFs.
全球变暖是人类必须共同面对的危机。温室气体(GHGs)是导致全球变暖的主要因素,因此采用相关工艺消除温室气体至关重要。金属有机框架(MOFs)具有高比表面积、大孔隙率和可调合成等优点,在温室气体储存、吸附、分离和催化等方面备受关注。然而,随着新合成和新发现的出现,MOFs 的数量迅速增加,为特定应用找到合适的 MOFs 极具挑战性。在这方面,高通量计算筛选被认为是筛选大量材料以发现高性能目标 MOF 的最有效研究方法。通常,高通量计算筛选会产生大量多维数据,非常适合机器学习(ML)训练,以提高筛选效率并深入探索多维数据之间的关系。本综述总结了在温室气体去除领域使用 ML 筛选 MOFs 的一般流程和常用方法。同时还探讨了 ML 在探索 MOF 空间时所面临的挑战,以及未来 ML 在 MOF 筛选方面的潜在发展方向。旨在加深对 ML 与 MOFs 在各领域结合的理解,拓宽 MOFs 的应用和发展思路。
{"title":"Efficient Removal of Greenhouse Gases: Machine Learning-Assisted Exploration of Metal-Organic Framework Space.","authors":"Ruiqi Xin, Chaohai Wang, Yingchao Zhang, Rongfu Peng, Rui Li, Junning Wang, Yanli Mao, Xinfeng Zhu, Wenkai Zhu, Minjun Kim, Ho Ngoc Nam, Yusuke Yamauchi","doi":"10.1021/acsnano.4c04174","DOIUrl":"https://doi.org/10.1021/acsnano.4c04174","url":null,"abstract":"<p><p>Global warming is a crisis that humanity must face together. With greenhouse gases (GHGs) as the main factor causing global warming, the adoption of relevant processes to eliminate them is essential. With the advantages of high specific surface area, large pore volume, and tunable synthesis, metal-organic frameworks (MOFs) have attracted much attention in GHG storage, adsorption, separation, and catalysis. However, as the pool of MOFs expands rapidly with new syntheses and discoveries, finding a suitable MOF for a particular application is highly challenging. In this regard, high-throughput computational screening is considered the most effective research method for screening a large number of materials to discover high-performance target MOFs. Typically, high-throughput computational screening generates voluminous and multidimensional data, which is well suited for machine learning (ML) training to improve the screening efficiency and explore the relationships between the multidimensional data in depth. This Review summarizes the general process and common methods for using ML to screen MOFs in the field of GHG removal. It also addresses the challenges faced by ML in exploring the MOF space and potential directions for the future development of ML for MOF screening. This aims to enhance the understanding of the integration of ML and MOFs in various fields and broaden the application and development ideas of MOFs.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Transarterial chemoembolization (TACE), the mainstay treatment of unresectable primary liver cancer that primarily employs nondegradable drug-loaded embolic agents to achieve synergistic vascular embolization and locoregional chemotherapy effects, suffers from an inferior drug burst behavior lacking long-term drug release controllability that severely limits the TACE efficacy. Here we developed gelatin-based drug-eluting microembolics grafted with nanosized poly(acrylic acid) serving as a biodegradable ion-exchange platform that leverages a counterion condensation effect to achieve high-efficiency electrostatic drug loading with electropositive drugs such as doxorubicin (i.e., drug loading capacity >34 mg/mL, encapsulation efficiency >98%, and loading time <10 min) and an enzymatic surface-erosion degradation pattern (∼2 months) to offer sustained locoregional pharmacokinetics with long-lasting deep-tumor retention capability for TACE treatment. The microembolics demonstrated facile microcatheter deliverability in a healthy porcine liver embolization model, superior tumor-killing capacity in a rabbit VX2 liver cancer embolization model, and stabilized extravascular drug penetration depth (>3 mm for 3 months) in a rabbit ear embolization model. Importantly, the microembolics finally exhibited vessel remodeling-induced permanent embolization with minimal inflammation responses after complete degradation. Such a biodegradable ion-exchange drug carrier provides an effective and versatile strategy for enhancing long-term therapeutic responses of various local chemotherapy treatments.
{"title":"Biodegradable Microembolics with Nanografted Polyanions Enable High-Efficiency Drug Loading and Sustained Deep-Tumor Drug Penetration for Locoregional Chemoembolization Treatment.","authors":"Yutao Ma, Zhihua Li, Yucheng Luo, Yao Chen, Le Ma, Xiaoya Liu, Jingyu Xiao, Man Huang, Yingnan Li, Hongliang Jiang, Meijuan Wang, Xiaoqian Wang, Jiangtao Li, Jian Kong, Peng Shi, Hanry Yu, Xingyu Jiang, Qiongyu Guo","doi":"10.1021/acsnano.4c00047","DOIUrl":"https://doi.org/10.1021/acsnano.4c00047","url":null,"abstract":"<p><p>Transarterial chemoembolization (TACE), the mainstay treatment of unresectable primary liver cancer that primarily employs nondegradable drug-loaded embolic agents to achieve synergistic vascular embolization and locoregional chemotherapy effects, suffers from an inferior drug burst behavior lacking long-term drug release controllability that severely limits the TACE efficacy. Here we developed gelatin-based drug-eluting microembolics grafted with nanosized poly(acrylic acid) serving as a biodegradable ion-exchange platform that leverages a counterion condensation effect to achieve high-efficiency electrostatic drug loading with electropositive drugs such as doxorubicin (i.e., drug loading capacity >34 mg/mL, encapsulation efficiency >98%, and loading time <10 min) and an enzymatic surface-erosion degradation pattern (∼2 months) to offer sustained locoregional pharmacokinetics with long-lasting deep-tumor retention capability for TACE treatment. The microembolics demonstrated facile microcatheter deliverability in a healthy porcine liver embolization model, superior tumor-killing capacity in a rabbit VX2 liver cancer embolization model, and stabilized extravascular drug penetration depth (>3 mm for 3 months) in a rabbit ear embolization model. Importantly, the microembolics finally exhibited vessel remodeling-induced permanent embolization with minimal inflammation responses after complete degradation. Such a biodegradable ion-exchange drug carrier provides an effective and versatile strategy for enhancing long-term therapeutic responses of various local chemotherapy treatments.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":null,"pages":null},"PeriodicalIF":15.8,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141464299","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}