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Functional Nanostructured Materials—from Synthesis to Applications

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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Synthesis, Interfaces and Nanostructures".

Deadline for manuscript submissions: closed (31 December 2022) | Viewed by 30851

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Special Issue Editors

Prof. Dr. Grzegorz Sulka

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Faculty of Chemistry, Department of Physical Chemistry & Electrochemistry Jagiellonian University in Krakow, Gronostajowa 2, 30-387 Krakow, Poland
Interests: nanostructured biomaterials; nanomaterials for energy conversion and storage; synthesis and applications of nanomaterials
Special Issues, Collections and Topics in MDPI journals

Dr. Agnieszka Brzózka

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Faculty of Chemistry, Department of Physical Chemistry & Electrochemistry Jagiellonian University in Krakow, Gronostajowa 2, 30-387 Krakow, Poland
Interests: nanomaterials for energy conversion and storage

Dr. Magdalena Jarosz

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Faculty of Chemistry, Department of Physical Chemistry & Electrochemistry Jagiellonian University in Krakow, Gronostajowa 2, 30-387 Krakow, Poland
Interests: nanostructured biomaterials

Dr. Karolina Syrek

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Guest Editor

Faculty of Chemistry, Department of Physical Chemistry, Electrochemistry Jagiellonian University in Krakow, Gronostajowa 2, 30-387 Krakow, Poland
Interests: synthesis and applications of nanomaterials; titania nanostructures; electrochemical synthesis; photoelectrochemistry

Special Issue Information

Dear Colleagues,

We would like to invite all researchers in the field of functional nanostructured materials to submit their original research papers for this Special Issue to be published in Nanomaterials, which will explore this topic in detail.

The scope of this Special Issue covers all aspects of the synthesis, characterization, and applications of functional nanostructured materials in three main aspects:

The synthesis and applications of nanomaterials. We are looking for manuscripts that are dedicated to the recent progress in all aspects related to functional nanomaterials, including methods of their synthesis and characterization and their possible applications. We especially encourage papers that are devoted to all electrochemical aspects connected to nanomaterials, including electrochemical methods used for nanofabrication, electrochemical techniques employed for the characterization of nanostructured materials, and applications of nanomaterials in electrochemistry.

Nanomaterials for energy conversion and storage. We welcome manuscripts related to the recent progress in the synthesis, modification, and characterization of nanomaterials for energy conversion and storage. This includes, but is not limited to, fundamental and applied studies on novel functional materials that can be used in photoelectrochemical and electrochemical energy conversion, fuel cells, and energy storage systems, such as batteries and supercapacitors.

Nanostructured biomaterials. We are looking for papers that research various nanomaterials (e.g., polymers, ceramics, and metals) that may be used as biomaterials, the requirements they must meet, and the problems that may be encountered with their use. Approaches from different fields of science (e.g., chemistry, engineering, and medicine) for the design, characterization, modification, and use of nanoscaled biomaterials will be considered.

This Special Issue will contain full papers, short communications, reviews, and mini-reviews. We warmly encourage you to submit a manuscript to this Special Issue regarding one of the aforementioned topics.

Prof. Dr. Grzegorz Sulka
Dr. Agnieszka Brzózka
Dr. Magdalena Jarosz
Dr. Karolina Syrek
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Nanomaterials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

nanomaterial synthesis
nanomaterial characterization
nanostructured biomaterials
nanomaterials for energy conversion
nanomaterials for energy storage
functional nanomaterials

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Published Papers (10 papers)

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Research

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14 pages, 3590 KiB

Open AccessArticle

Interpretation of Reflection and Colorimetry Characteristics of Indium-Particle Films by Means of Ellipsometric Modeling

by Hao-Tian Zhang, Rong He, Lei Peng, Yu-Ting Yang, Xiao-Jie Sun, Yu-Shan Zhang, Yu-Xiang Zheng, Bao-Jian Liu, Rong-Jun Zhang, Song-You Wang, Jing Li, Young-Pak Lee and Liang-Yao Chen

Nanomaterials 2023, 13(3), 383; https://doi.org/10.3390/nano13030383 - 18 Jan 2023

Cited by 3 | Viewed by 1823

Abstract

It is of great technological importance in the field of plasmonic color generation to establish and understand the relationship between optical responses and the reflectance of metallic nanoparticles. Previously, a series of indium nanoparticle ensembles were fabricated using electron beam evaporation and inspected using spectroscopic ellipsometry (SE). The multi-oscillator Lorentz–Drude model demonstrated the optical responses of indium nanoparticles with different sizes and size distributions. The reflectance spectra and colorimetry characteristics of indium nanoparticles with unimodal and bimodal size distributions were interpreted based on the SE analysis. The trends of reflectance spectra were explained by the transfer matrix method. The effects of optical constants n and k of indium on the reflectance were demonstrated by mapping the reflectance contour lines on the n-k plane. Using oscillator decomposition, the influence of different electron behaviors in various indium structures on the reflectance spectra was revealed intuitively. The contribution of each oscillator on the colorimetry characteristics, including hue, lightness and saturation, were determined and discussed from the reflectance spectral analysis. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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13 pages, 414 KiB

Open AccessArticle

Band Gap Tuning in Transition Metal and Rare-Earth-Ion-Doped TiO₂, CeO₂, and SnO₂ Nanoparticles

by Iliana Apostolova, Angel Apostolov and Julia Wesselinowa

Nanomaterials 2023, 13(1), 145; https://doi.org/10.3390/nano13010145 - 28 Dec 2022

Cited by 13 | Viewed by 3205

Abstract

The energy gap

E_{g}

between the valence and conduction bands is a key characteristic of semiconductors. Semiconductors, such as TiO

_{2}

, SnO

_{2}

, and CeO

_{2}

have a relatively wide band gap

E_{g}

that only allows the material to [...] Read more.

The energy gap

E_{g}

between the valence and conduction bands is a key characteristic of semiconductors. Semiconductors, such as TiO

_{2}

, SnO

_{2}

, and CeO

_{2}

have a relatively wide band gap

E_{g}

that only allows the material to absorb UV light. Using the s-d microscopic model and the Green’s function method, we have shown two possibilities to reduce the band-gap energy

E_{g}

—reducing the NP size and/or ion doping with transition metals (Co, Fe, Mn, and Cu) or rare earth (Sm, Tb, and Er) ions. Different strains appear that lead to changes in the exchange-interaction constants, and thus to a decrease in

E_{g}

. Moreover, the importance of the s-d interaction, which causes room-temperature ferromagnetism and band-gap energy tuning in dilute magnetic semiconductors, is shown. We tried to clarify some discrepancies in the experimental data. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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17 pages, 1825 KiB

Open AccessArticle

From Solid-State Cluster Compounds to Functional PMMA-Based Composites with UV and NIR Blocking Properties, and Tuned Hues

by Maria Amela-Cortes, Maxence Wilmet, Samuel Le Person, Soumaya Khlifi, Clément Lebastard, Yann Molard and Stéphane Cordier

Nanomaterials 2023, 13(1), 144; https://doi.org/10.3390/nano13010144 - 28 Dec 2022

Viewed by 2177

Abstract

New nanocomposite materials with UV-NIR blocking properties and hues ranging from green to brown were prepared by integrating inorganic tantalum octahedral cluster building blocks prepared via solid-state chemistry in a PMMA matrix. After the synthesis by the solid-state chemical reaction of the K₄[{Ta₆Brⁱ₁₂}Br^a₆] ternary halide, built-up from [{Ta₆Brⁱ₁₂}Br^a₆]⁴⁻ anionic building blocks, and potassium cations, the potassium cations were replaced by functional organic cations (Kat⁺) bearing a methacrylate function. The resulting intermediate, (Kat)₂[{Ta₆Brⁱ₁₂}Br^a₆], was then incorporated homogeneously by copolymerization with MMA into transparent PMMA matrices to form a brown transparent hybrid composite Ta@PMMA_brown. The color of the composites was tuned by controlling the charge and consequently the oxidation state of the cluster building block. Ta@PMMA_green was obtained through the two-electron reduction of the [{Ta₆Brⁱ₁₂}Br^a₆]²⁻ building blocks from Ta@PMMA_brown in solution. Indeed, the control of the oxidation state of the Ta₆ cluster inorganic building blocks occurred inside the copolymer, which not only allowed the tuning of the optical properties of the composite in the visible region but also allowed the tuning of its UV and NIR blocking properties. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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13 pages, 2746 KiB

Open AccessArticle

Deep-Level Emission Tailoring in ZnO Nanostructures Grown via Hydrothermal Synthesis

by Svetlana A. Kadinskaya, Valeriy M. Kondratev, Ivan K. Kindyushov, Olga Yu. Koval, Dmitry I. Yakubovsky, Alexey Kusnetsov, Alexey I. Lihachev, Alexey V. Nashchekin, Irina Kh. Akopyan, Alexey Yu. Serov, Mariana E. Labzovskaya, Sergey V. Mikushev, Boris V. Novikov, Igor V. Shtrom and Alexey D. Bolshakov

Nanomaterials 2023, 13(1), 58; https://doi.org/10.3390/nano13010058 - 23 Dec 2022

Cited by 14 | Viewed by 2696

Abstract

Zinc oxide (ZnO) nanostructures are widely used in various fields of science and technology due to their properties and ease of fabrication. To achieve the desired characteristics for subsequent device application, it is necessary to develop growth methods allowing for control over the nanostructures’ morphology and crystallinity governing their optical and electronic properties. In this work, we grow ZnO nanostructures via hydrothermal synthesis using surfactants that significantly affect the growth kinetics. Nanostructures with geometry from nanowires to hexapods are obtained and studied with photoluminescence (PL) spectroscopy. Analysis of the photoluminescence spectra demonstrates pronounced exciton on a neutral donor UV emission in all of the samples. Changing the growth medium chemical composition affects the emission characteristics sufficiently. Apart the UV emission, nanostructures synthesized without the surfactants demonstrate deep-level emission in the visible range with a peak near 620 nm. Structures synthesized with the use of sodium citrate exhibit emission peak near 520 nm, and those with polyethylenimine do not exhibit the deep-level emission. Thus, we demonstrate the correlation between the hydrothermal growth conditions and the obtained ZnO nanostructures’ optical properties, opening up new possibilities for their precise control and application in nanophotonics, UV–Vis and white light sources. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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21 pages, 10925 KiB

Open AccessArticle

Stabilization of an Aqueous Bio-Based Wax Nano-Emulsion through Encapsulation

by Pieter Samyn and Vibhore K. Rastogi

Nanomaterials 2022, 12(23), 4329; https://doi.org/10.3390/nano12234329 - 6 Dec 2022

Cited by 15 | Viewed by 5622

Abstract

The emulsification of biowaxes in an aqueous environment is important to broaden their application range and make them suitable for incorporation in water-based systems. The study here presented proposes a method for emulsification of carnauba wax by an in-situ imidization reaction of ammonolysed styrene (maleic anhydride), resulting in the encapsulation of the wax into stabilized organic nanoparticles. A parameter study is presented on the influences of wax concentrations (30 to 80 wt.-%) and variation in reaction conditions (degree of imidization) on the stability and morphology of the nanoparticles. Similar studies are done for encapsulation and emulsification of paraffin wax as a reference material. An analytical analysis with Raman spectroscopy and infrared spectroscopy indicated different reactivity of the waxes towards encapsulation, with the bio-based carnauba wax showing better compatibility with the formation of imidized styrene (maleic anhydride) nanoparticles. The latter can be ascribed to the higher functionality of the carnauba wax inducing more interactions with the organic nanoparticle phase compared to paraffin wax. In parallel, the thermal and mechanical stability of nanoparticles with encapsulated carnauba wax is higher than paraffin wax, as studied by differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical analysis. In conclusion, a stable aqueous emulsion with a maximum of 70 wt.-% encapsulated carnauba wax was obtained, being distributed as a droplet phase in 200 nm organic nanoparticles. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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17 pages, 4886 KiB

Open AccessEditor’s ChoiceArticle

Application of Micro/Nanoporous Fluoropolymers with Reduced Bioadhesion in Digital Microfluidics

by Andreas Goralczyk, Sagar Bhagwat, Fadoua Mayoussi, Niloofar Nekoonam, Kai Sachsenheimer, Peilong Hou, Frederik Kotz-Helmer, Dorothea Helmer and Bastian E. Rapp

Nanomaterials 2022, 12(13), 2201; https://doi.org/10.3390/nano12132201 - 27 Jun 2022

Cited by 6 | Viewed by 3209

Abstract

Digital microfluidics (DMF) is a versatile platform for conducting a variety of biological and chemical assays. The most commonly used set-up for the actuation of microliter droplets is electrowetting on dielectric (EWOD), where the liquid is moved by an electrostatic force on a dielectric layer. Superhydrophobic materials are promising materials for dielectric layers, especially since the minimum contact between droplet and surface is key for low adhesion of biomolecules, as it causes droplet pinning and cross contamination. However, superhydrophobic surfaces show limitations, such as full wetting transition between Cassie and Wenzel under applied voltage, expensive and complex fabrication and difficult integration into already existing devices. Here we present Fluoropor, a superhydrophobic fluorinated polymer foam with pores on the micro/nanoscale as a dielectric layer in DMF. Fluoropor shows stable wetting properties with no significant changes in the wetting behavior, or full wetting transition, until potentials of 400 V. Furthermore, Fluoropor shows low attachment of biomolecules to the surface upon droplet movement. Due to its simple fabrication process, its resistance to adhesion of biomolecules and the fact it is capable of being integrated and exchanged as thin films into commercial DMF devices, Fluoropor is a promising material for wide application in DMF. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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21 pages, 6183 KiB

Open AccessArticle

In Vitro High-Throughput Toxicological Assessment of Nanoplastics

by Valentina Tolardo, Davide Magrì, Francesco Fumagalli, Domenico Cassano, Athanassia Athanassiou, Despina Fragouli and Sabrina Gioria

Nanomaterials 2022, 12(12), 1947; https://doi.org/10.3390/nano12121947 - 7 Jun 2022

Cited by 17 | Viewed by 3812

Abstract

Sub-micrometer particles derived from the fragmentation of plastics in the environment can enter the food chain and reach humans, posing significant health risks. To date, there is a lack of adequate toxicological assessment of the effects of nanoplastics (NPs) in mammalian systems, particularly in humans. In this work, we evaluated the potential toxic effects of three different NPs in vitro: two NPs obtained by laser ablation (polycarbonate (PC) and polyethylene terephthalate (PET1)) and one (PET2) produced by nanoprecipitation. The physicochemical characterization of the NPs showed a smaller size, a larger size distribution, and a higher degree of surface oxidation for the particles produced by laser ablation. Toxicological evaluation performed on human cell line models (HePG2 and Caco-2) showed a higher toxic effect for the particles synthesized by laser ablation, with PC more toxic than PET. Interestingly, on differentiated Caco-2 cells, a conventional intestinal barrier model, none of the NPs produced toxic effects. This work wants to contribute to increase knowledge on the potential risks posed by NPs. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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19 pages, 8347 KiB

Open AccessArticle

Optimization of Sulfonated Polycatechol:PEDOT Energy Storage Performance by the Morphology Control

by Anatoliy A. Vereshchagin, Vasiliy V. Potapenkov, Petr S. Vlasov, Daniil A. Lukyanov and Oleg V. Levin

Nanomaterials 2022, 12(11), 1917; https://doi.org/10.3390/nano12111917 - 3 Jun 2022

Cited by 3 | Viewed by 2277

Abstract

Anionic catechol-containing polymers represent a promising class of functional dopants for the capacity improvement of conductive polymers. For example, sulfonated poly(vinylcatechol) SPVC with outstanding theoretical capacity was used as a dopant for poly(ethylenedixythiophene) (PEDOT) conductive polymer, increasing its energy storage performance. However, such materials suffer from insufficient utilization of the theoretical capacity of SPVC originating from non-optimal morphology. In the present study, we performed systematic optimization of the composition and morphology of the PEDOT:SPVC material as a function of the deposition parameters to overcome this problem. As a result, a capacity of 95 mAh·g⁻¹ was achieved in a thin film demonstrating considerable electrochemical stability: 75% capacity retention after 100 cycles and 57% after 1000 cycles. Since the capacity was found to suffer from thickness limitation, a nanocomposite of PEDOT:SPVC and single-walled carbon nanotubes with high PEDOT:SPVC loading was fabricated, yielding the capacitance 178 F·g⁻¹ or 89 F·cm⁻². The capacity values exceed non-optimized film twofold for thin film and 1.33 times for nanocomposite with carbon nanotubes. The obtained results demonstrate the importance of fine-tuning of the composition and morphology of the PEDOT:SPVC materials to ensure optimal interactions between the redox/anionic and conductive components. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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19 pages, 5319 KiB

Open AccessEditor’s ChoiceArticle

Photoelectrochemical Performance of Nanotubular Fe₂O₃–TiO₂ Electrodes under Solar Radiation

by Monika Sołtys-Mróz, Karolina Syrek, Łukasz Pięta, Kamilla Malek and Grzegorz D. Sulka

Nanomaterials 2022, 12(9), 1546; https://doi.org/10.3390/nano12091546 - 3 May 2022

Cited by 12 | Viewed by 2384

Abstract

Fe₂O₃–TiO₂ materials were obtained by the cathodic electrochemical deposition of Fe on anodic TiO₂ at different deposition times (5–180 s), followed by annealing at 450 °C. The effect of the hematite content on the photoelectrochemical (PEC) activity of the received materials was studied. The synthesized electrodes were characterized by field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Raman spectroscopy, diffuse reflectance spectroscopy (DRS), Mott–Schottky analysis, and PEC measurements. It was shown that the amount of deposited iron (ca. 0.5 at.%–30 at.%) and, consequently, hematite after a final annealing increased with the extension of deposition time and directly affected the semiconducting properties of the hybrid material. It was observed that the flat band potential shifted towards more positive values, facilitating photoelectrochemical water oxidation. In addition, the optical band gap decreased from 3.18 eV to 2.77 eV, which resulted in enhanced PEC visible-light response. Moreover, the Fe₂O₃–TiO₂ electrodes were sensitive to the addition of glucose, which indicates that such materials may be considered as potential PEC sensors for the detection of glucose. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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Review

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15 pages, 1648 KiB

Open AccessReview

Nanoporous Stainless Steel Materials for Body Implants—Review of Synthesizing Procedures

by Metka Benčina, Ita Junkar, Alenka Vesel, Miran Mozetič and Aleš Iglič

Nanomaterials 2022, 12(17), 2924; https://doi.org/10.3390/nano12172924 - 25 Aug 2022

Cited by 16 | Viewed by 2606

Abstract

Despite the inadequate biocompatibility, medical-grade stainless steel materials have been used as body implants for decades. The desired biological response of surfaces to specific applications in the body is a highly challenging task, and usually not all the requirements of a biomaterial can be achieved. In recent years, nanostructured surfaces have shown intriguing results as cell selectivity can be achieved by specific surface nanofeatures. Nanoporous structures can be fabricated by anodic oxidation, which has been widely studied for titanium and its alloys, while no systematic studies are so far available for stainless steel (SS) materials. This paper reviews the current state of the art in the anodisation of SS; correlations between the parameters of anodic oxidation and the surface morphology are drawn. The results reported by various authors are scattered because of a variety of experimental configurations. A linear correlation between the pores’ diameter anodisation voltage was deduced, while no correlation with other processing parameters was found obvious. The analyses of available data indicated a lack of systematic experiments, which are recommended to understand the kinetics of pore formation and develop techniques for optimal biocompatibility of stainless steel. Full article

(This article belongs to the Special Issue Functional Nanostructured Materials—from Synthesis to Applications)

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