Bi3NbO7(abbreviated BNO) exhibits favorable visible light responsiveness and chemical stability as a photocatalyst, which could be utilized for the purification of aqueous environments. However, the high photogenerated carrier complexation rate severely restricts the photocatalytic reaction. In this work, the one-pot solvent method was used to improve the photocatalytic ability by preparing S-scheme heterojunction composite photocatalysts by adding urea. The characteristic lamellar structure of Bi2O2CO3(abbreviated BOC) can increase the specific surface area and provide more active sites for the photoreaction. The construction of the S-scheme heterojunction could promote effective charge transfer and consume the unnecessary electrons and holes; meanwhile, the whole system is maintained at a high redox level so as to oxidize and decompose the pollutants. The experimental results showed that nanometer-sized 1.2 Bi3NbO7/Bi2O2CO3(abbreviated 1.2BNO/BOC) possesses good degradation effects for the simulated pollutants, the degradation efficiency is significantly improved compared with pure BNO, and the photocatalyst exhibits good cyclic stability.
{"title":"S-Scheme Nanometer-Sized Bi3NbO7/Bi2O2CO3 Heterojunction Photocatalysts for Efficient Pollutant Degradation","authors":"Baolong Cui, Hanxiao Xue, Yue Pan, Yi Du","doi":"10.1021/acsanm.4c02457","DOIUrl":"https://doi.org/10.1021/acsanm.4c02457","url":null,"abstract":"Bi<sub>3</sub>NbO<sub>7</sub>(abbreviated BNO) exhibits favorable visible light responsiveness and chemical stability as a photocatalyst, which could be utilized for the purification of aqueous environments. However, the high photogenerated carrier complexation rate severely restricts the photocatalytic reaction. In this work, the one-pot solvent method was used to improve the photocatalytic ability by preparing S-scheme heterojunction composite photocatalysts by adding urea. The characteristic lamellar structure of Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>(abbreviated BOC) can increase the specific surface area and provide more active sites for the photoreaction. The construction of the S-scheme heterojunction could promote effective charge transfer and consume the unnecessary electrons and holes; meanwhile, the whole system is maintained at a high redox level so as to oxidize and decompose the pollutants. The experimental results showed that nanometer-sized 1.2 Bi<sub>3</sub>NbO<sub>7</sub>/Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>(abbreviated 1.2BNO/BOC) possesses good degradation effects for the simulated pollutants, the degradation efficiency is significantly improved compared with pure BNO, and the photocatalyst exhibits good cyclic stability.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this article, a hydrogen sensor with excellent performance was synthesized using the hydrothermal method, with Pd-modified WO3 nanoplates as the sensing layer. At an optimum operating temperature of 200 °C, the hydrogen gas sensing capabilities of WO3 and Pd-WO3 composite sensors were investigated. The findings indicate that in contrast to the WO3 sensor, the Pd-WO3 composite sensor exhibits superior hydrogen sensing performance, showcasing remarkable selectivity, reliable repeatability, sustained long-term stability, and quick response and recovery (8 s/10 s@100 ppm). The first-principles density functional theory was used to explain the sensing mechanism of the Pd-WO3 composite. The improved sensing performance of Pd-WO3 composite sensors was explained from the perspectives of the Schottky junction formed between Pd nanoparticles and WO3, the catalytic effect of metal Pd nanoparticles, and gas adsorption–desorption. This article confirms that Pd-modified WO3 nanoplates are good candidates for efficient hydrogen gas sensing.
{"title":"Pd-Doped WO3 Nanoplates for Hydrogen Sensing: Experimental Studies and Density Functional Theory Investigations","authors":"Shiteng Ma, Fengjiao Chen, Yukun Liu, Hao Zhang, Peilin Jia, Dongzhi Zhang","doi":"10.1021/acsanm.4c02114","DOIUrl":"https://doi.org/10.1021/acsanm.4c02114","url":null,"abstract":"In this article, a hydrogen sensor with excellent performance was synthesized using the hydrothermal method, with Pd-modified WO<sub>3</sub> nanoplates as the sensing layer. At an optimum operating temperature of 200 °C, the hydrogen gas sensing capabilities of WO<sub>3</sub> and Pd-WO<sub>3</sub> composite sensors were investigated. The findings indicate that in contrast to the WO<sub>3</sub> sensor, the Pd-WO<sub>3</sub> composite sensor exhibits superior hydrogen sensing performance, showcasing remarkable selectivity, reliable repeatability, sustained long-term stability, and quick response and recovery (8 s/10 s@100 ppm). The first-principles density functional theory was used to explain the sensing mechanism of the Pd-WO<sub>3</sub> composite. The improved sensing performance of Pd-WO<sub>3</sub> composite sensors was explained from the perspectives of the Schottky junction formed between Pd nanoparticles and WO<sub>3</sub>, the catalytic effect of metal Pd nanoparticles, and gas adsorption–desorption. This article confirms that Pd-modified WO<sub>3</sub> nanoplates are good candidates for efficient hydrogen gas sensing.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525244","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Due to oxygenation, carbon nanotubes cannot operate field emission for a long period of time. So far, the emission-induced oxygenation mechanism has not been studied in detail; particularly, the underlying mechanism that causes a drastic increase of the emitting current contiguous to the turn-on voltage remains unclear. Cold plasma is a nonthermal equilibrium process and can also oxygenate carbon materials through radiolysis. In this work, electrical measurements of single-walled carbon nanotubes are in situ carried out in O2 and N2 plasma irradiation, and the tube resistance due to irradiative damages is found to increase in three steps, defined as regions I, II, and III. In region I, the increase is rapid and involves extraction of intercalated O2 between the nanotubes. The nanotubes become severely oxygenated in region II, thus enhancing the on-tube scattering and resistance. Nanotube segmentation takes place in region III, where the opened edges are likely bonded with oxygenated and nitride groups. Experimental data successfully explain the field emission instability of carbon nanotubes, including a low life cycle, sudden increase in emitting current around the turn-on voltage, and thermal decomposition of carbon lattices.
由于氧合作用，碳纳米管无法长时间进行场发射。迄今为止，人们尚未对发射诱导氧合机制进行详细研究，尤其是导致发射电流在接通电压下急剧增加的根本机制仍不清楚。冷等离子体是一种非热平衡过程，也可以通过辐射分解使碳材料富氧。在这项工作中，我们在 O2 和 N2 等离子辐照下对单壁碳纳米管进行了原位电学测量，发现辐照损伤导致的管电阻增加分为三个步骤，分别定义为区域 I、区域 II 和区域 III。在区域 I 中，增加速度很快，涉及纳米管之间夹杂的 O2 的提取。在区域 II 中，纳米管严重含氧，从而增强了管上散射和电阻。纳米管分割发生在区域 III，打开的边缘可能与含氧基团和氮化物基团结合。实验数据成功地解释了碳纳米管的场发射不稳定性，包括低生命周期、开启电压附近发射电流的突然增加以及碳晶格的热分解。
{"title":"In Situ Electrical Characterization of Carbon Nanotubes in O2 and N2 Plasma to Explain their Field Emission Instability","authors":"Yen-Hung Kuo, Jen-Kuang Fang, Jen-Chun Chen, Pai-Sheng Shih, Ping-Chun Chen, Yung-Kai Yang, Hsin-Jung Tsai, Wen-Kuang Hsu","doi":"10.1021/acsanm.4c02655","DOIUrl":"https://doi.org/10.1021/acsanm.4c02655","url":null,"abstract":"Due to oxygenation, carbon nanotubes cannot operate field emission for a long period of time. So far, the emission-induced oxygenation mechanism has not been studied in detail; particularly, the underlying mechanism that causes a drastic increase of the emitting current contiguous to the turn-on voltage remains unclear. Cold plasma is a nonthermal equilibrium process and can also oxygenate carbon materials through radiolysis. In this work, electrical measurements of single-walled carbon nanotubes are in situ carried out in O<sub>2</sub> and N<sub>2</sub> plasma irradiation, and the tube resistance due to irradiative damages is found to increase in three steps, defined as regions I, II, and III. In region I, the increase is rapid and involves extraction of intercalated O<sub>2</sub> between the nanotubes. The nanotubes become severely oxygenated in region II, thus enhancing the on-tube scattering and resistance. Nanotube segmentation takes place in region III, where the opened edges are likely bonded with oxygenated and nitride groups. Experimental data successfully explain the field emission instability of carbon nanotubes, including a low life cycle, sudden increase in emitting current around the turn-on voltage, and thermal decomposition of carbon lattices.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525253","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hongsheng Jia, Zhimeng Zhang, Siqi Li, Miao Han, Yuanlong E, Chunbo Liu, Qingshuang Wang, Wanqiang Liu
Due to the continuous depletion of lithium resources and the security risks of organic electrolytes such as combustion and explosion, there is an imminent requirement to develop a type of energy accumulation system to adapt to the progression and progress of society. Zinc-ion batteries using aqueous electrolyte have the advantages of high safety, low cost, and environmental friendliness, which make them an ideal alternative to lithium-ion batteries as a next-generation energy storage system. Among the zinc-ion battery cathode materials, manganese-based materials and carbon materials occupy the main positions, respectively. Among them, nickel manganate (NiMn2O4) nanosheets and carbon nanotubes (CNTs) as active materials have received extensive attention. The CNTs could provide electronic conductive channels and NiMn2O4 nanosheets supply more active points for electrochemical reactions. The carbon shell with a porous structure also improves the electron transport and ionic conduction processes, so that the nickel manganate/carbon nanotube (NiMn2O4/CNTs) nanocomposites obtained a high specific capacitance of 333.6 mAh g–1 at a current density of 0.2 A g–1. After 500 cycles at a current density of 0.5 A g–1 led to a high specific capacity of 73.6 mAh g–1, it was shown that the material exhibits excellent comprehensive electrochemical properties. This synergistic strategy of combining structural design and electrochemical activation in NiMn2O4/CNTs nanocomposites can be a reference for other manganese-based cathode materials.
由于锂资源的不断枯竭和有机电解质存在燃烧、爆炸等安全隐患，开发一种适应社会发展和进步的能量积累系统迫在眉睫。使用水性电解质的锌离子电池具有安全性高、成本低、环境友好等优点，是替代锂离子电池的下一代理想储能系统。在锌离子电池正极材料中，锰基材料和碳材料分别占据主要地位。其中，锰酸镍（NiMn2O4）纳米片和碳纳米管（CNTs）作为活性材料受到广泛关注。CNT 可提供电子导电通道，而 NiMn2O4 纳米片则为电化学反应提供了更多的活性点。具有多孔结构的碳外壳还能改善电子传输和离子传导过程，因此镍锰酸盐/碳纳米管（NiMn2O4/CNTs）纳米复合材料在 0.2 A g-1 的电流密度下获得了 333.6 mAh g-1 的高比电容。在 0.5 A g-1 的电流密度下循环 500 次后，比容量达到 73.6 mAh g-1，表明该材料具有优异的综合电化学性能。镍锰氧化物/碳纳米管纳米复合材料的结构设计与电化学活化相结合的协同策略可为其他锰基阴极材料提供参考。
{"title":"NiMn2O4 Nanosheet/Carbon Nanotube Composites for Aqueous Zinc-Ion Batteries","authors":"Hongsheng Jia, Zhimeng Zhang, Siqi Li, Miao Han, Yuanlong E, Chunbo Liu, Qingshuang Wang, Wanqiang Liu","doi":"10.1021/acsanm.4c02183","DOIUrl":"https://doi.org/10.1021/acsanm.4c02183","url":null,"abstract":"Due to the continuous depletion of lithium resources and the security risks of organic electrolytes such as combustion and explosion, there is an imminent requirement to develop a type of energy accumulation system to adapt to the progression and progress of society. Zinc-ion batteries using aqueous electrolyte have the advantages of high safety, low cost, and environmental friendliness, which make them an ideal alternative to lithium-ion batteries as a next-generation energy storage system. Among the zinc-ion battery cathode materials, manganese-based materials and carbon materials occupy the main positions, respectively. Among them, nickel manganate (NiMn<sub>2</sub>O<sub>4</sub>) nanosheets and carbon nanotubes (CNTs) as active materials have received extensive attention. The CNTs could provide electronic conductive channels and NiMn<sub>2</sub>O<sub>4</sub> nanosheets supply more active points for electrochemical reactions. The carbon shell with a porous structure also improves the electron transport and ionic conduction processes, so that the nickel manganate/carbon nanotube (NiMn<sub>2</sub>O<sub>4</sub>/CNTs) nanocomposites obtained a high specific capacitance of 333.6 mAh g<sup>–1</sup> at a current density of 0.2 A g<sup>–1</sup>. After 500 cycles at a current density of 0.5 A g<sup>–1</sup> led to a high specific capacity of 73.6 mAh g<sup>–1</sup>, it was shown that the material exhibits excellent comprehensive electrochemical properties. This synergistic strategy of combining structural design and electrochemical activation in NiMn<sub>2</sub>O<sub>4</sub>/CNTs nanocomposites can be a reference for other manganese-based cathode materials.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
LiNi0.8Co0.1Mn0.1O2 hollow micro–nano hierarchical microspheres (H-NCM811) were synthesized using multishelled hollow structured NiO microspheres as precursors with Co and Mn sources. The traditional synthetic methods of hollow structured NiO microspheres generally require complicated steps. Herein, a general and straightforward method is applied to synthesize the multishelled porous NiO microspheres by the hydrothermal method and calcination at high temperature. Compared to conventional cathode materials, the H-NCM811 cathode materials synthesized by the NiO hollow microsphere exhibit enhanced cycle stability. After 100 charge–discharge cycles at 1 C with a voltage range of 2.8–4.3 V, the capacity retention is 93.3%. Notably the capacity retention is 87.0% after 300 cycles at 5 C compared to 72.0% for the conventional NCM811. The enhanced electrochemical performance can be ascribed to the distinctive nanostructured hollow microsphere’s structure, which not only improves the discharge capacity by the higher specific surface area but also can provide a buffer zone during the Li-ion extraction/insertion process and maintain the structure stability.
以多壳空心结构氧化镍微球为前驱体，以Co和Mn为源，合成了LiNi0.8Co0.1Mn0.1O2空心微纳分层微球（H-NCM811）。传统的空心结构氧化镍微球合成方法通常需要复杂的步骤。本文采用水热法和高温煅烧法合成多壳多孔镍氧化物微球，该方法简便易行。与传统的正极材料相比，由氧化镍空心微球合成的 H-NCM811 正极材料具有更高的循环稳定性。在电压范围为 2.8-4.3 V、温度为 1 C 的条件下进行 100 次充放电循环后，容量保持率为 93.3%。值得注意的是，在 5 C 下循环 300 次后，容量保持率为 87.0%，而传统 NCM811 的容量保持率为 72.0%。电化学性能的提高可归因于独特的纳米结构空心微球结构，这种结构不仅能通过较高的比表面积提高放电容量，还能在锂离子提取/插入过程中提供缓冲区并保持结构的稳定性。
{"title":"Nanostructured LiNi0.8Co0.1Mn0.1O2 with a Hollow Morphology Boosting Cycling Stability as Cathode Materials for Lithium-Ion Batteries","authors":"Fangya Guo, Zenan Hu, Yongfan Xie, Fang Wang","doi":"10.1021/acsanm.4c01979","DOIUrl":"https://doi.org/10.1021/acsanm.4c01979","url":null,"abstract":"LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> hollow micro–nano hierarchical microspheres (H-NCM811) were synthesized using multishelled hollow structured NiO microspheres as precursors with Co and Mn sources. The traditional synthetic methods of hollow structured NiO microspheres generally require complicated steps. Herein, a general and straightforward method is applied to synthesize the multishelled porous NiO microspheres by the hydrothermal method and calcination at high temperature. Compared to conventional cathode materials, the H-NCM811 cathode materials synthesized by the NiO hollow microsphere exhibit enhanced cycle stability. After 100 charge–discharge cycles at 1 C with a voltage range of 2.8–4.3 V, the capacity retention is 93.3%. Notably the capacity retention is 87.0% after 300 cycles at 5 C compared to 72.0% for the conventional NCM811. The enhanced electrochemical performance can be ascribed to the distinctive nanostructured hollow microsphere’s structure, which not only improves the discharge capacity by the higher specific surface area but also can provide a buffer zone during the Li-ion extraction/insertion process and maintain the structure stability.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525331","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The nanoparticle-induced endothelial leakiness effect can enhance the ability of nanoparticles (NPs) to cross the vascular barrier but also promote pathological processes. The rarity of NPs capable of endothelial penetration without adverse effects underscores a critical challenge. Addressing this, we designed a bivalve pH-responsive pathway that controlled self-shedding NPs. At its core lies a composite structure comprising indocyanine green-doped spiky SiO2 NPs within an inner-shell comprising the cationic polymer polyethylenimine (PEI), tethered to the core via hydrazone linkages, alongside the inclusion of the endothelial recovery factor angiopoietin-1 (Ang1) and an outermost biomimetic cell membrane shell. In drug delivery, our NPs can target and traverse the endothelial barrier. Then, the initiation of the first self-shedding process ensues upon exposure to an acidic milieu, eliciting the proton sponge effect facilitated by PEI, thereby inducing membrane rupture and enabling NP release, while at the same time, Ang1 is released to repair the disrupted endothelial barrier. Furthermore, the hydrazone bonds were broken in the more acidic environment closer to the tumor site to realize the second self-shedding process, which reproduced the spiky morphology for promoted endocytosis. Therefore, the designed self-shedding NPs can realize two steps of self-shedding to inhibit tumor metastasis and improve photothermal therapy.
{"title":"pH-Responsive Pathway-Controlled Layer-by-Layer Self-Shedding Nanoparticles for Endothelial Barrier Repair and Efficient Tumor-Targeted Therapy","authors":"Yuan Huang, Xilin Xiong, Bo Huang, Xinxin Luo, Qi Ke, Pengyu Wu, Hangxing Wang, Qichao Zou, Suxiao Wang, Limin Wu","doi":"10.1021/acsanm.4c01292","DOIUrl":"https://doi.org/10.1021/acsanm.4c01292","url":null,"abstract":"The nanoparticle-induced endothelial leakiness effect can enhance the ability of nanoparticles (NPs) to cross the vascular barrier but also promote pathological processes. The rarity of NPs capable of endothelial penetration without adverse effects underscores a critical challenge. Addressing this, we designed a bivalve pH-responsive pathway that controlled self-shedding NPs. At its core lies a composite structure comprising indocyanine green-doped spiky SiO<sub>2</sub> NPs within an inner-shell comprising the cationic polymer polyethylenimine (PEI), tethered to the core via hydrazone linkages, alongside the inclusion of the endothelial recovery factor angiopoietin-1 (Ang1) and an outermost biomimetic cell membrane shell. In drug delivery, our NPs can target and traverse the endothelial barrier. Then, the initiation of the first self-shedding process ensues upon exposure to an acidic milieu, eliciting the proton sponge effect facilitated by PEI, thereby inducing membrane rupture and enabling NP release, while at the same time, Ang1 is released to repair the disrupted endothelial barrier. Furthermore, the hydrazone bonds were broken in the more acidic environment closer to the tumor site to realize the second self-shedding process, which reproduced the spiky morphology for promoted endocytosis. Therefore, the designed self-shedding NPs can realize two steps of self-shedding to inhibit tumor metastasis and improve photothermal therapy.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mónica Gaspar Simões, Katrin Unger, Caterina Czibula, Anna Maria Coclite, Robert Schennach, Ulrich Hirn
Adhesion between solid materials is caused by intermolecular forces that only take place if the adhering surfaces are at nanoscale contact (NSC) (i.e., 0.1–0.4 nm. To study adhesion, NSC can be evaluated with Förster Resonance Energy Transfer (FRET). FRET uses the interaction of compatible fluorescence molecules to measure the nanometer distance between bonded surfaces. For this, each surface is labeled with one fluorescence dye, named the Donor or Acceptor. If these molecules are in NSC, a nonradiative Donor–Acceptor energy transfer will occur and can be detected using FRET spectroscopy. Here, for the first time, we introduce an innovative concept of a FRET-based NSC measurement employing dye-nanolayer films prepared by a physical vapor deposition (PVD). The dye nanolayers were prepared by PVD from the vaporization of the Donor and Acceptor molecules separately. The selected molecules, 7-Amino-4-methyl-cumarin (C120) and 5(6)-Carboxy-2′,7′-dichlor-fluorescein (CDCF), present high quantum yields (QY, QYD = 0.91 and QYA = 0.64) and a low FRET distance range of 0.6–2.2 nm, adequate for the study of NSC. The produced dye-nanolayer films exhibit a uniform dye distribution (verified by atomic force microscopy) and suitable fluorescence intensities. To validate the NSC measurements, FRET spectroscopy experiments were performed with bonded dye-nanolayer films prepared under different loads (from 1.5 to 140 bar), thus creating different degrees of NSC. The results show an increase in FRET intensity (R2 = 0.95) with the respective adhesion energy between the films, which is directly related to the degree of NSC. Hence, this work establishes FRET as an experimental technique for the measurement of NSC, and its relation to surface adhesion. Additionally, thanks to the FRET dye-nanolayer approach, the method can be employed on arbitrary surfaces. Essentially, any sufficiently transparent substrate can be functionalized with FRET compatible dyes to evaluate NSC, which represents a breakthrough in contact mechanics investigations of soft and hard solid materials.
{"title":"Functionalizing Surfaces by Physical Vapor Deposition To Measure the Degree of Nanoscale Contact Using FRET","authors":"Mónica Gaspar Simões, Katrin Unger, Caterina Czibula, Anna Maria Coclite, Robert Schennach, Ulrich Hirn","doi":"10.1021/acsanm.4c01809","DOIUrl":"https://doi.org/10.1021/acsanm.4c01809","url":null,"abstract":"Adhesion between solid materials is caused by intermolecular forces that only take place if the adhering surfaces are at nanoscale contact (NSC) (i.e., 0.1–0.4 nm. To study adhesion, NSC can be evaluated with Förster Resonance Energy Transfer (FRET). FRET uses the interaction of compatible fluorescence molecules to measure the nanometer distance between bonded surfaces. For this, each surface is labeled with one fluorescence dye, named the Donor or Acceptor. If these molecules are in NSC, a nonradiative Donor–Acceptor energy transfer will occur and can be detected using FRET spectroscopy. Here, for the first time, we introduce an innovative concept of a FRET-based NSC measurement employing dye-nanolayer films prepared by a physical vapor deposition (PVD). The dye nanolayers were prepared by PVD from the vaporization of the Donor and Acceptor molecules separately. The selected molecules, 7-Amino-4-methyl-cumarin (C120) and 5(6)-Carboxy-2′,7′-dichlor-fluorescein (CDCF), present high quantum yields (QY, QY<sub>D</sub> = 0.91 and QY<sub>A</sub> = 0.64) and a low FRET distance range of 0.6–2.2 nm, adequate for the study of NSC. The produced dye-nanolayer films exhibit a uniform dye distribution (verified by atomic force microscopy) and suitable fluorescence intensities. To validate the NSC measurements, FRET spectroscopy experiments were performed with bonded dye-nanolayer films prepared under different loads (from 1.5 to 140 bar), thus creating different degrees of NSC. The results show an increase in FRET intensity (<i>R</i><sup>2</sup> = 0.95) with the respective adhesion energy between the films, which is directly related to the degree of NSC. Hence, this work establishes FRET as an experimental technique for the measurement of NSC, and its relation to surface adhesion. Additionally, thanks to the FRET dye-nanolayer approach, the method can be employed on arbitrary surfaces. Essentially, any sufficiently transparent substrate can be functionalized with FRET compatible dyes to evaluate NSC, which represents a breakthrough in contact mechanics investigations of soft and hard solid materials.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ravina Beniwal, Debasish Biswasray, Pratiksha Gawas, Aswathy S., Shadak Alee K., Christopher E. Petoukhoff, Venkatramaiah Nutalapati, Bala Murali Krishna Mariserla
Graphene’s exceptional efficacies for optoelectronic and photonic applications have captivated the world toward technological advancements. However, its atomic-scale thickness impedes light–matter interactions and limits device performances. Recently, graphene adorned with metallic nanoparticles has gained huge attention for its potential to improve the optical absorption in a broad spectral range. Herein, we have enhanced the optical absorption by in situ grown silver and gold nanoparticles on simultaneously reduced graphene oxide nanosheets using nanosecond laser pulses. Plasmon field distributions and interfacial interactions were simulated through finite difference time domain calculations for hybrids, as well as individual metal nanoparticles. Also, extinction cross sections of nanoparticles and reduced graphene oxide nanosheets along with hybrids were simulated to compare with the experimental results, and we found an enriched optical response due to the interaction of the localized plasmon resonance band of metal nanoparticles with broad absorption of reduced graphene oxide nanosheets. We explored the I–V characteristics, particularly at surface plasmon resonance wavelengths, to capture the plasmon effect on device performance and found an enhanced photocurrent for hybrids. The charge transfer and free carrier absorption in these hybrids have shown a giant nonlinear optical absorption in the nanosecond regime. The observed optoelectronic responses of these hybrid materials are well-suited for light sensing and optical safety devices.
{"title":"Laser Driven In Situ Growth of Metal Nanoparticles on Graphene Oxide Nanosheets for Plasmon-Enhanced Optoelectronic Responses","authors":"Ravina Beniwal, Debasish Biswasray, Pratiksha Gawas, Aswathy S., Shadak Alee K., Christopher E. Petoukhoff, Venkatramaiah Nutalapati, Bala Murali Krishna Mariserla","doi":"10.1021/acsanm.4c01452","DOIUrl":"https://doi.org/10.1021/acsanm.4c01452","url":null,"abstract":"Graphene’s exceptional efficacies for optoelectronic and photonic applications have captivated the world toward technological advancements. However, its atomic-scale thickness impedes light–matter interactions and limits device performances. Recently, graphene adorned with metallic nanoparticles has gained huge attention for its potential to improve the optical absorption in a broad spectral range. Herein, we have enhanced the optical absorption by <i>in situ</i> grown silver and gold nanoparticles on simultaneously reduced graphene oxide nanosheets using nanosecond laser pulses. Plasmon field distributions and interfacial interactions were simulated through finite difference time domain calculations for hybrids, as well as individual metal nanoparticles. Also, extinction cross sections of nanoparticles and reduced graphene oxide nanosheets along with hybrids were simulated to compare with the experimental results, and we found an enriched optical response due to the interaction of the localized plasmon resonance band of metal nanoparticles with broad absorption of reduced graphene oxide nanosheets. We explored the <i>I</i>–<i>V</i> characteristics, particularly at surface plasmon resonance wavelengths, to capture the plasmon effect on device performance and found an enhanced photocurrent for hybrids. The charge transfer and free carrier absorption in these hybrids have shown a giant nonlinear optical absorption in the nanosecond regime. The observed optoelectronic responses of these hybrid materials are well-suited for light sensing and optical safety devices.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymersomes have been studied for many years since their discovery, and have consistently been an appealing and widely explored research domain. Their inherent benefits, encompassing stability, versatility, load-carrying capacity, and deformability, endow them with many opportunities to be used in numerous fields of biomedicine, nanocarriers, diagnostics and therapeutics. Nevertheless, shape transformation pathways have not been comprehensively summarized or received adequate scholarly attention. Herein, we summarize typical mechanisms underlying polymersome self-assembly with a particular focus on the shape transformation pathways associated with commonly employed self-assembling methods. Moreover, we provide a succinct overview of the proposed applications involving shape transformation applications, and enumerate the most recent findings in this domain.
{"title":"Review of Shape Transformation Pathways of Polymersomes: Implications for Nanomotor, Biomedicine, and Artificial Cell Mimics","authors":"Xurui Zhang, Jan C. M. van Hest, Yongjun Men","doi":"10.1021/acsanm.4c02200","DOIUrl":"https://doi.org/10.1021/acsanm.4c02200","url":null,"abstract":"Polymersomes have been studied for many years since their discovery, and have consistently been an appealing and widely explored research domain. Their inherent benefits, encompassing stability, versatility, load-carrying capacity, and deformability, endow them with many opportunities to be used in numerous fields of biomedicine, nanocarriers, diagnostics and therapeutics. Nevertheless, shape transformation pathways have not been comprehensively summarized or received adequate scholarly attention. Herein, we summarize typical mechanisms underlying polymersome self-assembly with a particular focus on the shape transformation pathways associated with commonly employed self-assembling methods. Moreover, we provide a succinct overview of the proposed applications involving shape transformation applications, and enumerate the most recent findings in this domain.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Madhureeta Das Gupta, Brian O. Patrick, Jolene P. Reid, Mark J. MacLachlan
Multicomponent supramolecular self-assembled systems can potentially harness the properties of multiple systems simultaneously. However, creating multicomponent supramolecular nanostructures with narrow size distributions is challenging due to the dynamic nature of noncovalent interactions. In this article, we report the coassembly of a tris-Ni(II)-salphen and a tris-Cu(II)-salphen complex. Co-assembly of the complexes afforded nanofibers with low dispersity, with the metal complexes homogeneously distributed throughout the nanofibers. The length of the nanofibers could also be tuned by varying the ratio of the metal complexes. Density functional theory (DFT) calculations indicate that the dimerization of the copper(II) complex is unfavorable, unlike the dimerization of the nickel(II) complex. Co-assembly with the copper(II) complex inhibits the self-assembly of the nickel(II) complex, enabling length control of the bimetallic nanofibers. These results could pave the way for designing multicomponent supramolecular systems with applications in catalysis and magnetic devices.
{"title":"Benzene-1,3,5-tricarboxamide Metal Complexes Self-Assembled in Nanofibers: Implications for Bimetallic Catalytic Nanomaterials","authors":"Madhureeta Das Gupta, Brian O. Patrick, Jolene P. Reid, Mark J. MacLachlan","doi":"10.1021/acsanm.4c01485","DOIUrl":"https://doi.org/10.1021/acsanm.4c01485","url":null,"abstract":"Multicomponent supramolecular self-assembled systems can potentially harness the properties of multiple systems simultaneously. However, creating multicomponent supramolecular nanostructures with narrow size distributions is challenging due to the dynamic nature of noncovalent interactions. In this article, we report the coassembly of a tris-Ni(II)-salphen and a tris-Cu(II)-salphen complex. Co-assembly of the complexes afforded nanofibers with low dispersity, with the metal complexes homogeneously distributed throughout the nanofibers. The length of the nanofibers could also be tuned by varying the ratio of the metal complexes. Density functional theory (DFT) calculations indicate that the dimerization of the copper(II) complex is unfavorable, unlike the dimerization of the nickel(II) complex. Co-assembly with the copper(II) complex inhibits the self-assembly of the nickel(II) complex, enabling length control of the bimetallic nanofibers. These results could pave the way for designing multicomponent supramolecular systems with applications in catalysis and magnetic devices.","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":null,"pages":null},"PeriodicalIF":5.9,"publicationDate":"2024-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141525337","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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