ACS Nano最新文献

{"title":"Pt@WS2 Mott–Schottky Heterojunction Boosts Light-Driven Active Ion Transport for Enhanced Ionic Power Harvesting","authors":"Pan Jia, Zhitong Han, Jiansheng Chen, Junchao Liu, Lina Wang, Xinyi Zhang, Yue Guo, Jinming Zhou","doi":"10.1021/acsnano.4c15723","DOIUrl":"https://doi.org/10.1021/acsnano.4c15723","url":null,"abstract":"Bioinspired light-driven ion transport in two-dimensional (2D) nanofluidics offers exciting prospects for solar energy harvesting. Current single-component nanofluidic membranes often suffer from low light-induced driving forces due to the easy recombination of photogenerated electron–hole pairs. Herein, we present a Pt@WS₂ Mott–Schottky heterojunction-based 2D nanofluidic membrane for boosting light-driven active ion transport and solar enhanced ionic power harvesting. The photovoltaic effect in the Mott–Schottky heterojunctions and photoconductance effect in WS₂ multilayers account for more efficient charge separation across the nanofluidic membrane. In an equilibrium electrolyte solution, we observe directional cationic transport from the WS₂ to the Pt region under visible-light illumination. In 10^–3 M KCl electrolyte, the photocurrent and photovoltage reach 11.84 μA cm^–2 and 30.67 mV, respectively. Moreover, the output power can reach up to 5.02 W m^–2 under light illumination, compared to a value of 2.56 W m^–2 without irradiation. This work not only introduces a driving mechanism for boosting ion transport but also offers a pathway for integrating multiple energy sources.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"87 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833081","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}

{"title":"In Vivo Surface-Enhanced Transmission Raman Spectroscopy and Impact of Frozen Biological Tissues on Lesion Depth Prediction","authors":"Yutong Zhou, Yumin Zhang, Haoqiang Xie, Zongyu Wu, Bowen Shi, Linley Li Lin, Jian Ye","doi":"10.1021/acsnano.4c12469","DOIUrl":"https://doi.org/10.1021/acsnano.4c12469","url":null,"abstract":"Plasmonic surface-enhanced transmission Raman spectroscopy (SETRS) has emerged as a promising optical technique for detecting and predicting the depths of deep-seated lesions in biological tissues. However, <i>in vivo</i> studies using SETRS are scarce and typically show shallow penetration depths. Moreover, the optical parameters used in the prediction process are often derived from frozen samples and there is limited understanding of how freezing affects the optical properties of biological tissues and the accuracy of depth prediction in living models. In this work, we conduct <i>in vivo</i> SETRS measurements on thick abdominal tissue region of the live rats to investigate the impact of freezing on the measured optical properties for the purpose of depth prediction. First, we fabricated ultrahigh bright surface-enhanced Raman spectroscopy (SERS) nanotags and utilized a custom transmission Raman system. We then measured the change of optical attenuation at two different wavelengths (Δ<i>μ</i>) for four types of rat tissues (including skin, fat, muscle, and liver) following freezing. The freezing process dramatically affects Δ<i>μ</i> values, even after only 1 day of freezing. In contrast, Δ<i>μ</i> values obtained from fresh samples enable precise localization of SERS lesion phantoms in the live rat with only 5% deviation. The total thickness of the live rat is 2.6 cm, which, to the best of our knowledge, is the highest value of <i>in vivo</i> SETRS studies so far. This work helps to fill the gap in the SERS field of tissue localization and optical coefficient studies in highly heterogeneous tissues, and demonstrates the potential of the SETRS technique to achieve precise clinical localization of deep lesions.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"8 7 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833076","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}

{"title":"Enhanced Gut-to-Liver Oral Drug Delivery via Ligand-Modified Nanoparticles by Attenuating Protein Corona Adsorption","authors":"Jie Wang, Zilong Zhang, Zhuan Zhang, Zhiwen Zou, Yan Zhuo, Chang Liu, Di Nie, Yong Gan, Miaorong Yu","doi":"10.1021/acsnano.4c11453","DOIUrl":"https://doi.org/10.1021/acsnano.4c11453","url":null,"abstract":"The development of effective oral drug delivery systems for targeted gut-to-liver transport remains a significant challenge due to the multiple biological barriers including the harsh gastrointestinal tract (GIT) environment and the complex protein corona (PC) formation. In this study, we developed ligand-modified nanoparticles (NPs) that enable gut-to-liver drug delivery by crossing the GIT and attenuating PC formation. Specifically, mesoporous silica nanoparticles (MSNs) were functionalized with peptides targeting the neonatal Fc receptor (FcRn), capitalizing on FcRn expression in the small intestine and liver for targeted drug delivery. We showed that MSNs decorated with a small cyclic FcRn binding peptide (MSNs-FcBP) obtained enhanced diffusion in intestinal mucus and superior transportation across the intestine compared to unmodified MSNs and MSNs decorated with a large IgG Fc fragment (MSNs-Fc), which correlated with diminished protein adsorption and weaker interaction with mucin. After entering the blood circulation, reduced serum PC formation by MSNs-FcBP reduces the proteolytic and phagocytic propensity of the reticuloendothelial system, ultimately ameliorating accumulation in hepatocytes. Pharmacokinetic and pharmacodynamic studies in diabetic mice revealed that MSNs-FcBP effectively transported the therapeutic agent exenatide across the intestinal epithelium, leading to a significant hypoglycemic response and improved glucose tolerance. This study underscores the critical role of ligand selection in limiting protein corona formation, thereby significantly enhancing gut-to-liver drug delivery by increasing mucus permeation and minimizing serum–protein interactions. The effective delivery of exenatide in diabetic mice illustrates the potential of this strategy to optimize oral drug bioavailability and therapeutic efficacy.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"50 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833040","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}

{"title":"Bright Quantum-Grade Fluorescent Nanodiamonds","authors":"Keisuke Oshimi, Hitoshi Ishiwata, Hiromu Nakashima, Sara Mandić, Hina Kobayashi, Minori Teramoto, Hirokazu Tsuji, Yoshiki Nishibayashi, Yutaka Shikano, Toshu An, Masazumi Fujiwara","doi":"10.1021/acsnano.4c03424","DOIUrl":"https://doi.org/10.1021/acsnano.4c03424","url":null,"abstract":"Optically accessible spin-active nanomaterials are promising as quantum nanosensors for probing biological samples. However, achieving bioimaging-level brightness and high-quality spin properties for these materials is challenging and hinders their application in quantum biosensing. Here, we demonstrate bright fluorescent nanodiamonds (NDs) containing 0.6–1.3-ppm negatively charged nitrogen-vacancy (NV) centers by spin-environment engineering via enriching spin-less &lt;sup&gt;12&lt;/sup&gt;C-carbon isotopes and reducing substitutional nitrogen spin impurities. The NDs, readily introduced into cultured cells, exhibited improved optically detected magnetic resonance (ODMR) spectra; peak splitting (&lt;i&gt;E&lt;/i&gt;) was reduced by 2–3 MHz, and microwave excitation power required was 20 times lower to achieve a 3% ODMR contrast, comparable to that of conventional type-Ib NDs. They show average spin-relaxation times of &lt;i&gt;T&lt;/i&gt;&lt;sub&gt;1&lt;/sub&gt; = 0.68 ms and &lt;i&gt;T&lt;/i&gt;&lt;sub&gt;2&lt;/sub&gt; = 3.2 μs (1.6 ms and 5.4 μs maximum) that were 5- and 11-fold longer than those of type-Ib, respectively. Additionally, the extended &lt;i&gt;T&lt;/i&gt;&lt;sub&gt;2&lt;/sub&gt; relaxation times of these NDs enable shot-noise-limited temperature measurements with a sensitivity of approximately &lt;i&gt;&lt;/i&gt;&lt;span style=\"color: inherit;\"&gt;&lt;/span&gt;&lt;span data-mathml='&lt;math xmlns=\"http://www.w3.org/1998/Math/MathML\" display=\"inline\"&gt;&lt;mn&gt;0.28&lt;/mn&gt;&lt;mspace width=\"0.25em\" /&gt;&lt;mi mathvariant=\"normal\"&gt;K&lt;/mi&gt;&lt;mo&gt;/&lt;/mo&gt;&lt;msqrt&gt;&lt;mi&gt;Hz&lt;/mi&gt;&lt;/msqrt&gt;&lt;/math&gt;' role=\"presentation\" style=\"position: relative;\" tabindex=\"0\"&gt;&lt;nobr aria-hidden=\"true\"&gt;&lt;span style=\"width: 5.685em; display: inline-block;\"&gt;&lt;span style=\"display: inline-block; position: relative; width: 5.173em; height: 0px; font-size: 110%;\"&gt;&lt;span style=\"position: absolute; clip: rect(1.423em, 1005.17em, 3.014em, -999.997em); top: -2.554em; left: 0em;\"&gt;&lt;span&gt;&lt;span style=\"font-family: STIXMathJax_Main;\"&gt;0.28&lt;/span&gt;&lt;span style=\"height: 0em; vertical-align: 0em; width: 0.287em; display: inline-block; overflow: hidden;\"&gt;&lt;/span&gt;&lt;span style=\"font-family: STIXMathJax_Main;\"&gt;K&lt;span style=\"display: inline-block; overflow: hidden; height: 1px; width: 0.003em;\"&gt;&lt;/span&gt;&lt;/span&gt;&lt;span style=\"font-family: STIXMathJax_Main;\"&gt;/&lt;/span&gt;&lt;span&gt;&lt;span style=\"display: inline-block; position: relative; width: 2.105em; height: 0px;\"&gt;&lt;span style=\"position: absolute; clip: rect(3.128em, 1001.14em, 4.151em, -999.997em); top: -3.974em; left: 0.912em;\"&gt;&lt;span&gt;&lt;span style=\"font-family: STIXMathJax_Main;\"&gt;Hz&lt;/span&gt;&lt;/span&gt;&lt;span style=\"display: inline-block; width: 0px; height: 3.98em;\"&gt;&lt;/span&gt;&lt;/span&gt;&lt;span style=\"position: absolute; clip: rect(3.526em, 1001.2em, 3.923em, -999.997em); top: -4.599em; left: 0.912em;\"&gt;&lt;span style=\"display: inline-block; position: relative; width: 1.196em; height: 0px;\"&gt;&lt;span style=\"position: absolute; font-family: STIXMathJax_Symbols; top: -3.974em; left: 0em;\"&gt;⎯&lt;span style=\"display: inline-block; width: 0px; height: 3.98em;\"&gt;","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"37 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832901","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}

{"title":"Spatiotemporal Mapping of Lymphatic Metastases in Gastric Cancer Using Tumor-Trackable and Enzyme-Activatable Near-Infrared Fluorescent Nanoprobes","authors":"Mengya Yu, Lijuan Zhu, Guoqi Dong, Jianjiao Chen, Bankang Ruan, Yi Liu, Shujuan Yi, Zhenqi Meng, Guanjian Chen, Weiping Xu, Jiaguo Huang, Fanghai Han","doi":"10.1021/acsnano.4c12915","DOIUrl":"https://doi.org/10.1021/acsnano.4c12915","url":null,"abstract":"Sentinel lymph node biopsy holds significant importance in cancer management, yet the challenge persists in early detection and precise resection of metastasis lymph nodes (LNs) due to the absence of specific and sensitive optical probes. This study reports metastatic LN reporters (MLRs) with an activatable optical output for accurate spatiotemporal mapping of lymphatic metastases in gastric cancer. MLRs are self-assembled entities incorporating mixed amphiphiles with a lipophilic tail and a tumor-targeting ligand or a fluorescent moiety that is caged with a switch cleavable by tumor-specific β-galactosidase (β-Gal). After draining into LNs, MLRs selectively activate their near-infrared fluorescence in the presence of spreading tumor cells. In orthotopic gastric cancer mouse models, the representative reporter MLR1 distinguishes macro/micrometastatic LNs from benign LNs and enables early detection of skip LNs metastasis patterns in a spatial-dependent manner. Such an active sensing mechanism provides a high level of sensitivity and specificity comparable to those of flow cytometry analysis. In surgically resected patient specimens, MLR1 differentiates cancerous tissues and metastatic LNs from normal tissues and benign LNs within 1 h. This study thus presents NIRF nanoprobes that permit facile detection of LN metastases in GC patient samples and highlights a generic translatable nanoprobe design for understanding metastatic progression.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"19 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833080","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}

{"title":"Molecular Engineering to Construct MoS2 with Expanded Interlayer Spacing and Enriched 1T Phase for “Rocking-Chair” Aqueous Calcium-Ion Pouch Cells","authors":"Wenhao Wang, Wenwei Zhang, Ruohan Yu, Fan Qiao, Jilin Wang, Junjun Wang, Qinyou An","doi":"10.1021/acsnano.4c11147","DOIUrl":"https://doi.org/10.1021/acsnano.4c11147","url":null,"abstract":"The moderate working voltage and high capacity of transition metal dichalcogenides (TMDs) make them promising anode materials for aqueous calcium-ion batteries (ACIBs). However, the large radius and two charges of Ca²⁺ cause TMDs to exhibit poor performance in ACIBs. Therefore, effective regulation strategies are crucial for enabling the application of TMDs in ACIBs. Herein, MoS₂ with expanded interlayer spacing and an enriched 1T phase (ES-1T-MoS₂) is constructed by molecular engineering and reported as an anode material for ACIBs. Molecular engineering increases the capacity of MoS₂ from 29.4 to 91.2 mAh g^–1 and improves its rate performance from 20 to 76.1 mAh g^–1 at 2.0 A g^–1. ES-1T-MoS₂ also shows a −20 to 50 °C wide temperature working capability. Furthermore, the capacity improvement reasons and the calcium storage mechanism of ES-1T-MoS₂ are revealed through density functional theory calculations and <i>in situ</i>/<i>ex situ</i> characterizations. Finally, a “rocking-chair” aqueous calcium-ion pouch cell with a Prussian blue analogue cathode and ES-1T-MoS₂ anode is assembled. The pouch cell exhibits a life of 150 cycles with over 90.8% capacity retention at 0 and 25 °C. This work demonstrates that molecular engineering is an effective strategy to improve the calcium storage performance of TMDs and promotes the advancement of ACIBs.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"10 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833077","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}

{"title":"Biomimetic Nanostructured Polyimine Aerogels with Graded Porosity, Flame Resistance, Intrinsic Superhydrophobicity, and Closed-Loop Recovery","authors":"Hongfei He, Lu Liu, Hongliang Ding, Chuanshen Wang, Ping Yu, Chao Ding, Jixin Zhu, Wei Yang, Yuan Hu, Bin Yu","doi":"10.1021/acsnano.4c12853","DOIUrl":"https://doi.org/10.1021/acsnano.4c12853","url":null,"abstract":"Polymer aerogels, with their porous and lightweight features, excel in applications such as energy storage, absorption, and thermal insulation, making them a sought-after new material. However, the covalent cross-linking networks of current polymer aerogels result in unsustainable manufacturing and processing practices, persistently depleting our finite natural resources and causing significant global environmental impacts. Herein, we have constructed a high-performance dynamic covalent cross-linking aerogel network using biobased materials, with its structure and green sustainability akin to those of plants in nature. Abundant reversible cross-linking points endow the aerogel with ultrafast degradation capabilities, enabling allow for closed-loop chemical monomer recovery and reprocessing. Furthermore, utilizing the highly active reversible network, net-zero emission material reuse and reprocessing can be achieved. Additionally, the controlled dynamic aerogel network features a multilevel roughness nanostructured surface similar to lotus leaf and a biomimetic pore structure, contributing to significant anisotropy. The distinctive structure and composition endow the dynamic aerogel with high compressive strength (2.2 MPa) vertically, low thermal conductivity (0.0257 W/(m·K)) horizontally, and outstanding fire resistance (LOI is as high as 36%). Notably, the aerogel demonstrates the highest hydrophobicity among polyimine materials, with a contact angle of 154°. Furthermore, those dynamic aerogels have excellent performance in a variety of potential applications such as oil–water separation, directional transport, and phase change energy storage, and it is anticipated that these applications will greatly benefit from systematic upgrades in recyclability and reprocessing.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"61 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832889","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}

{"title":"Single-Molecule Multivalent Interactions Revealed by Plasmon-Enhanced Fluorescence","authors":"Kasper R. Okholm, Sjoerd W. Nooteboom, Johan Nygaard Vinther, Vincenzo Lamberti, Swayandipta Dey, Ebbe Sloth Andersen, Peter Zijlstra, Duncan S. Sutherland","doi":"10.1021/acsnano.4c12600","DOIUrl":"https://doi.org/10.1021/acsnano.4c12600","url":null,"abstract":"Multivalency as an interaction principle is widely utilized in nature. It enables specific and strong binding by multiple weak interactions through enhanced avidity and is a core process in immune recognition and cellular signaling, which is also a current concept in drug design. Here, we use the high signals from plasmon-enhanced fluorescence of nanoparticles to extract binding kinetics and dynamics of multivalent interactions on the single-molecule level and in real time. We study mono-, bi-, and trivalent binding interactions using a DNA Holliday Junction as a model construct with programmable valency and introduce a step-binding model for binding kinetics relevant for structured macromolecules by including an experimentally extractable binding restriction term ω to quantify the effects from conformation, steric effects, and rigidity. We used this approach to explore how length and flexibility of the DNA ligands affect binding restriction and binding strength, where the overall binding strength decreased with spacer length. For trivalent systems, increasing spacer length additionally activated binding in the trivalent state, giving insight into the design of multivalent drug or targeting moieties. By systematically changing the receptor density, we explored the binding super selectivity of the multivalent HJ at the single-molecule level. We find a polynomial behavior of the trivalent binding strength that clearly shows receptor-density-dependent selective binding. Interestingly, we could exploit the rapidly decaying near fields of the plasmon that induce a strong dependence of the signal on the position of the dye to observe binding dynamics during single multivalent binding events.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"25 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833078","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}

{"title":"Metal Nanoclusters for Interface Engineering and Improved Photovoltaic Performance in Organic Solar Cells","authors":"Yousuf Alishan, Alvin Joseph, Anitha B. Pillai, Ravari Kandy Aparna, Ranjini Sarkar, Sudip Chakraborty, Sukhendu Mandal, Manoj A. G. Namboothiry","doi":"10.1021/acsnano.4c12256","DOIUrl":"https://doi.org/10.1021/acsnano.4c12256","url":null,"abstract":"Copper nanoclusters (Cu NCs), synthesized by a one-pot synthesis method, were theoretically shown to exhibit a dipole moment and cause work function modification on a surface as observed from Kelvin probe measurement. Here, Cu NCs were used as an interfacial modifier in organic solar cells (OSCs). The effective engineering of the electron transporting layer/active layer interface using Cu NCs resulted in improved photovoltaic performance in fullerene and non-fullerene based OSCs. On insertion of Cu NCs, the best power conversion efficiency (PCE) obtained for the non-fullerene based system was 15.83% compared to 14.22% for the control device, while the PCE increased from 7.79% to 8.62% for the fullerene based system. The interface modification resulted in reduced recombination losses and charge accumulation at the interfaces. The improved performance in Cu NC interfaced devices is attributed to work function modification, enabling reduced energy barrier and enhanced charge collection.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"6 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833052","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}

{"title":"Structural, Electrochemical, and (De)lithiation Mechanism Investigation of Cation-Disordered Rocksalt and Spinel Hybrid Nanomaterials in Lithium-Ion Batteries","authors":"Arun Kingan, Cynthia Huang, Zachary R. Mansley, Ryan C. Hill, Zhongling Wang, David C. Bock, Lei Wang, Lu Ma, Steven N. Ehrlich, Jianming Bai, Hui Zhong, Cherno Jaye, Conan Weiland, Amy C. Marschilok, Esther S. Takeuchi, Yimei Zhu, Shan Yan, Kenneth J. Takeuchi","doi":"10.1021/acsnano.4c11725","DOIUrl":"https://doi.org/10.1021/acsnano.4c11725","url":null,"abstract":"Significant demand for lithium-ion batteries necessitates alternatives to Co- and Ni-based cathode materials. Cation-disordered materials using earth-abundant elements are being explored as promising candidates. In this paper, we demonstrate a coprecipitation synthetic approach that allows direct preparation of disordered rocksalt Li_2.4Fe_1.0Ti_1.0O_4.7 (r-LFTO·C) and spinel structured hybrid Li_0.5Fe_1.0Ti_0.9O_3.2·C (s-LFTO·C) nanoparticles with a conformal conductive carbon coating. High-angle annular dark-field imaging coupled with electron energy loss spectroscopy mapping shows uniform Fe/Ti distribution with minor compositional variation among particles. Cation disorder was confirmed for both of the materials at an atomic level, with a short-range order more pronounced in r-LFTO·C. Operando X-ray absorption spectroscopy, ex situ hard X-ray photoelectron spectroscopy, ex situ soft X-ray absorption spectroscopy, and ex situ synchrotron X-ray diffraction were used to investigate (de)lithiation in the bulk and at the surface. Structurally, the r-LFTO·C demonstrated reversible partial Fe center migration between octahedral and tetrahedral sites during (de)lithiation. The r-LFTO·C evidenced that the redox of O was coincident with iron redox during initial electrochemical cycling, while iron redox dominated later cycling. In contrast, s-LFTO·C electrochemistry involved iron redox throughout the cycling process. The findings rationalize the differences in the electrochemistry where r-LFTO·C shows higher initial capacity yet poorer capacity retention over a voltage window where O redox can be accessed, while the s-LFTO·C shows lower initial capacity yet improved capacity retention.","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":"29 1","pages":""},"PeriodicalIF":17.1,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816069","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}