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Preparation and Characterization of Nanomaterials with Multifunctional Properties

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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Nanofabrication and Nanomanufacturing".

Deadline for manuscript submissions: closed (30 June 2022) | Viewed by 28989

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Prof. Dr. Félix Zamora

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1. Departamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain
2. Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid, 28049 Madrid, Spain
3. Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid, 28049 Madrid, Spain
Interests: nanomaterials; 2D materials; porous materials
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Dr. Carmen Montoro

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Inorganic Chemistry Department, Universidad Autónoma de Madrid, Madrid, Spain
Interests: metal/covalent organic frameworks; capture and degradation of pollutants; water remediation; processing of porous materials for practical applications
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Multifunctional nanomaterials have become an increasingly popular field of research over the past few decades due to the significant changes in physical and/or chemical properties that occur at this small scale. Specifically, it has been seen that interesting modifications take place in magnetic, electronic, optical, and catalytic properties, among others, with respect to materials of larger dimensions. Accordingly, nanomaterials are used in a variety of applications, including catalysis, gas storage, spin crossover, sensors, magnetics, optics, and drug delivery.

This Special Issue of Nanomaterials will present recent innovative scientific works, collected from both academia and industry, that describe the state of the art of nanomaterials with multifunctional properties. Moreover, it is expected to present an overview of different methods used for the preparation and characterization of nanomaterials for potential applications.

The readers will find relevant information regarding some of the following topics:

Synthesis of multifunctional nanomaterials;
Organic/inorganic multifunctional nanocomposites;
New characterization techniques for functional nanomaterials;
Theoretical studies and modeling;
Nanocomposites and their applications;
Stimuli-responsive nanosystems;
Catalysis;
Bionanomaterials.

Finally, we would like to invite you to submit your manuscript to this Special Issue by sending a communication or a full paper from your group or a review article on some of these topics. We are looking forward to receiving your contributions.

Prof. Dr. Félix Zamora
Dr. Carmen Montoro
Guest Editors

Manuscript Submission Information

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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 2900 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.

Published Papers (11 papers)

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Research

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13 pages, 3382 KiB

Open AccessArticle

3D Printing of Ultrathin MXene toward Tough and Thermally Resistant Nanocomposites

by Yuewei Li, Ranjith Kumar Kankala, Ai-Zheng Chen and Shi-Bin Wang

Nanomaterials 2022, 12(16), 2862; https://0-doi-org.brum.beds.ac.uk/10.3390/nano12162862 - 19 Aug 2022

Viewed by 1666

Abstract

Liquid crystal display (LCD)-based 3D printing, a facile and cost-effective manufacturing technique, is often applied when fabricating objects with porcelain structures using photosensitive resins (PSRs). Currently, 3D printed constructions are typically used as models for demonstration purposes rather than industrial applications because of their poor performance. In this study, we prepared nanocomposites by incorporating Ti₃C₂ MXene nanosheets to enhance the overall characteristics of a PSR, including mechanical properties and thermal resistance. Notably, the designed nanocomposites showed optimum performance at an MXene loading of 0.5% w/w. The mechanical properties of the designed nanocomposites confirmed the enhanced ultimate tensile and flexural strengths (by 32.1% and 42.7%, respectively), at 0.5% w/w MXene loading. Moreover, the incorporated MXene presented no substantial influence on the toughness of the PSR. The glass transition and thermal degradation temperatures at 5% weight loss increased by 7.4 and 10.6 °C, respectively, resulting predominantly from the hydrogen bonding between the PSR and MXene. Together, the experimental results indicate that the designed PSR/MXene nanocomposites are expected to replace pristine resins for LCD printing in various practical applications. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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13 pages, 3515 KiB

Open AccessArticle

Manufacturing a TiO₂-Based Semiconductor Film with Nanofluid Pool Boiling and Sintering Processes toward Solar-Cell Applications

by Saeid Vafaei, Ian Holmes, Benjamin Errion, Zigmey Thukka, Ryoki Narita, Takashi Sugiura and Kazuhiro Manseki

Nanomaterials 2022, 12(7), 1165; https://0-doi-org.brum.beds.ac.uk/10.3390/nano12071165 - 31 Mar 2022

Cited by 5 | Viewed by 1527

Abstract

For the first time, nanofluid boiling was applied as a process for the creation of a semiconductor TiO₂ nanoparticle film that can be deposited onto a conductive substrate (F-doped SnO₂ glass: FTO). A steel-base device designed for pool boiling was used to deposit a TiO₂-based nanofluid consisting of nanoparticles with an average size of about 20 nm. The boiling of the nanofluid directly on the FTO glass substrate allowed for the deposition of the nanoparticles onto the FTO surface. In principle, the surface responsible for transferring heat to the fluid can be covered with these nanoparticles when the nanofluid boils. Using the as-deposited films, crystal growth of the TiO₂ nanoparticle was controlled by varying the strategies of the post-sintering profile. The maximum temperatures, periods, and ramping rates for the obtained samples were systematically changed. Scanning electron microscopy (SEM) revealed that a densely packed TiO₂-nanoparticle layer was obtained for the as-deposited substrate via pool boiling. For the maximum temperature at 550 °C, the TiO₂ grain sizes became larger (~50 nm) and more round-shaped TiO₂ nanostructures were identified. Notably, we have demonstrated for the first time how the sintering of TiO₂ nanoparticles proceeds for the nanoporous TiO₂ films using high-resolution transmission electron microscopy (TEM) measurements. We found that the TiO₂ nanoparticles fused with each other and crystal growth occurred through neighboring 2–4 nanoparticles for the 550 °C sample, which was proved by the TEM analysis that continuous lattice fringes corresponding to the (101) anatase phase were clearly observed through the entire area of some nanoparticles aligned horizontally. In addition, the loss of the TiO₂ nanofluid (precursor solution) was completely avoided in our TiO₂ deposition. Unlike the commonly used spin-coating method, nanofluid pool boiling would provide an alternative cost-effective approach to manufacture semiconductor layers for various applications, such as solar cells. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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21 pages, 3335 KiB

Open AccessArticle

Tailoring Interfacial Exchange Anisotropy in Hard–Soft Core-Shell Ferrite Nanoparticles for Magnetic Hyperthermia Applications

by Venkatesha Narayanaswamy, Imaddin A. Al-Omari, Aleksandr S. Kamzin, Bashar Issa and Ihab M. Obaidat

Nanomaterials 2022, 12(2), 262; https://0-doi-org.brum.beds.ac.uk/10.3390/nano12020262 - 14 Jan 2022

Cited by 10 | Viewed by 1830

Abstract

Magnetically hard–soft core-shell ferrite nanoparticles are synthesized using an organometallic decomposition method through seed-mediated growth. Two sets of core-shell nanoparticles (S1 and S2) with different shell (Fe₃O₄) thicknesses and similar core (CoFe₂O₄) sizes are obtained by varying the initial quantities of seed nanoparticles of size 6.0 ± 1.0 nm. The nanoparticles synthesized have average sizes of 9.5 ± 1.1 (S1) and 12.2 ± 1.7 (S2) nm with corresponding shell thicknesses of 3.5 and 6.1 nm. Magnetic properties are investigated under field-cooled and zero-field-cooled conditions at several temperatures and field cooling values. Magnetic heating efficiency for magnetic hyperthermia applications is investigated by measuring the specific absorption rate (SAR) in alternating magnetic fields at several field strengths and frequencies. The exchange bias is found to have a nonmonotonic and oscillatory relationship with temperature at all fields. SAR values of both core-shell samples are found to be considerably larger than that of the single-phase bare core particles. The effective anisotropy and SAR values are found to be larger in S2 than those in S1. However, the saturation magnetization displays the opposite behavior. These results are attributed to the occurrence of spin-glass regions at the core-shell interface of different amounts in the two samples. The novel outcome is that the interfacial exchange anisotropy of core-shell nanoparticles can be tailored to produce large effective magnetic anisotropy and thus large SAR values. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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19 pages, 10254 KiB

Open AccessArticle

Effect of the Processing on the Resistance–Strain Response of Multiwalled Carbon Nanotube/Natural Rubber Composites for Use in Large Deformation Sensors

by Xingyao Liu, Rongxin Guo, Rui Li, Hui Liu, Zhengming Fan, Yang Yang and Zhiwei Lin

Nanomaterials 2021, 11(7), 1845; https://0-doi-org.brum.beds.ac.uk/10.3390/nano11071845 - 16 Jul 2021

Cited by 16 | Viewed by 2212

Abstract

The dispersion, electrical conductivities, mechanical properties and resistance–strain response behaviors of multiwalled carbon nanotube (MWCNT)/natural rubber (NR) composites synthesized by the different processing conditions are systematically investigated at both macro- and micro-perspectives. Compared with the solution and flocculation methods, the two roll method produced the best MWCNTs distribution since the materials are mixed by strong shear stress between the two rolls. An excellent segregated conductive network is formed and that a low percolation threshold is obtained (~1 wt.%) by the two roll method. Different from the higher increases in conductivity for the composites obtained by the solution and flocculation methods when the MWCNT content is higher than 3 wt.%, the composite prepared by the two roll method displays obvious improvements in its mechanical properties. In addition, the two roll method promotes good stability, repeatability, and durability along with an ultrahigh sensitivity (GF_max = 974.2) and a large strain range (ε = 109%). The ‘shoulder peak’ phenomenon has not been observed in the composite prepared by the two roll method, confirming its potential for application as a large deformation monitoring sensor. Moreover, a mathematical model is proposed to explain the resistance–strain sensing mechanism. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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22 pages, 2744 KiB

Open AccessArticle

A Deep Learning Approach for Molecular Classification Based on AFM Images

by Jaime Carracedo-Cosme, Carlos Romero-Muñiz and Rubén Pérez

Nanomaterials 2021, 11(7), 1658; https://0-doi-org.brum.beds.ac.uk/10.3390/nano11071658 - 24 Jun 2021

Cited by 16 | Viewed by 3659

Abstract

In spite of the unprecedented resolution provided by non-contact atomic force microscopy (AFM) with CO-functionalized and advances in the interpretation of the observed contrast, the unambiguous identification of molecular systems solely based on AFM images, without any prior information, remains an open problem. This work presents a first step towards the automatic classification of AFM experimental images by a deep learning model trained essentially with a theoretically generated dataset. We analyze the limitations of two standard models for pattern recognition when applied to AFM image classification and develop a model with the optimal depth to provide accurate results and to retain the ability to generalize. We show that a variational autoencoder (VAE) provides a very efficient way to incorporate, from very few experimental images, characteristic features into the training set that assure a high accuracy in the classification of both theoretical and experimental images. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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14 pages, 7231 KiB

Open AccessArticle

Preparation and Properties of Electrospun Phenylethynyl—Terminated Polyimide Nano-Fibrous Membranes with Potential Applications as Solvent-Free and High-Temperature Resistant Adhesives for Harsh Environments

by Hao-ran Qi, Deng-xiong Shen, Yan-jiang Jia, Yuan-cheng An, Hao Wu, Xin-ying Wei, Yan Zhang, Xin-xin Zhi and Jin-gang Liu

Nanomaterials 2021, 11(6), 1525; https://0-doi-org.brum.beds.ac.uk/10.3390/nano11061525 - 09 Jun 2021

Cited by 3 | Viewed by 2099

Abstract

High-temperature-resistant polymeric adhesives with high servicing temperatures and high adhesion strengths are highly desired in aerospace, aviation, microelectronic and other high-tech areas. The currently used high-temperature resistant polymeric adhesives, such as polyamic acid (PAA), are usually made from the high contents of solvents in the composition, which might cause adhesion failure due to the undesirable voids caused by the evaporation of the solvents. In the current work, electrospun preimidized polyimide (PI) nano-fibrous membranes (NFMs) were proposed to be used as solvent-free or solvent-less adhesives for stainless steel adhesion. In order to enhance the adhesion reliability of the PI NFMs, thermally crosslinkable phenylethynyl end-cappers were incorporated into the PIs derived from 3,3’,4,4’-oxydiphthalic anhydride (ODPA) and 3,3-bis[4-(4-aminophenoxy)phenyl]phthalide (BAPPT). The derived phenylethynyl-terminated PETI-10K and PETI-20K with the controlled molecular weights of 10,000 g mol⁻¹ and 20,000 g mol⁻¹, respectively, showed good solubility in polar aprotic solvents, such as N-methyl-2-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc). The PI NFMs were successfully fabricated by electrospinning with the PETI/DMAc solutions. The ultrafine PETI NFMs showed the average fiber diameters (d_av) of 627 nm for PETI-10K 695 nm for PETI-20K, respectively. The PETI NFMs showed good thermal resistance, which is reflected in the glass transition temperatures (T_gs) above 270 °C. The PETI NFMs exhibited excellent thermoplasticity at elevated temperatures. The stainless steel adherends were successfully adhered using the PETI NFMs as the adhesives. The PI NFMs provided good adhesion to the stainless steels with the single lap shear strengths (LSS) higher than 20.0 MPa either at room temperature (25 °C) or at an elevated temperature (200 °C). Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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13 pages, 1731 KiB

Open AccessEditor’s ChoiceArticle

Magnetism and ε-τ Phase Transformation in MnAl-Based Nanocomposite Magnets

by Alina Daniela Crisan, Aurel Leca, Cristina Bartha, Ioan Dan and Ovidiu Crisan

Nanomaterials 2021, 11(4), 896; https://0-doi-org.brum.beds.ac.uk/10.3390/nano11040896 - 31 Mar 2021

Cited by 3 | Viewed by 1920

Abstract

Melt spun ribbons of Mn₅₃Al₄₅C₂ and Mn₅₂Al₄₆C₂ have been synthesized by rapid quenching of the melt with the purpose of monitoring the ε-τ phase transformation to show technologically feasible ways to increase magnetic parameters and to illustrate the viability of these alloys as the next generation of rare earth (RE)-free magnets. By differential scanning calorimetry (DSC), activation energies and temperatures of onset of the ε-τ phase transformation were obtained. Structural analysis was performed using X-ray diffraction (XRD) and the resulting XRD patterns were quantitatively assessed using full profile Rietveld-type analysis. Appropriate annealing was performed in order to enable the ε-τ phase transformation. While hcp ε-phase was found to be predominant in the as-cast samples, after appropriate annealing, the tetragonal τ-phase, the one that furnishes the relevant magnetic response, was found to be predominant with an abundance of about 90%. The data suggested a mechanism of hcp ε-phase decomposition controlled by the segregation towards the interfacial regions, having the rate of transformation governed by antiphase boundary diffusion processes. Magnetic measurements of annealed sample Mn₅₃Al₄₅C₂, consisting of predominant tetragonal τ-phase, showed high values of magnetization and increased coercivity, consistent with an energy product of about 10 MGOe, similar with previously reported magnetization measurements, providing further insight into the realization of future class of RE-free low-cost permanent magnets. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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15 pages, 3006 KiB

Open AccessArticle

Degradable Spirocyclic Polyacetal-Based Core-Amphiphilic Assemblies for Encapsulation and Release of Hydrophobic Cargo

by Brandon Andrade-Gagnon, Marilyne Bélanger-Bouliga, Phuong Trang Nguyen, Thi Hong Diep Nguyen, Steve Bourgault and Ali Nazemi

Nanomaterials 2021, 11(1), 161; https://0-doi-org.brum.beds.ac.uk/10.3390/nano11010161 - 10 Jan 2021

Cited by 6 | Viewed by 2531

Abstract

Polymeric nanomaterials that degrade in acidic environments have gained considerable attention in nanomedicine for intracellular drug delivery and cancer therapy. Among various acid-degradable linkages, spirocyclic acetals have rarely been used to fabricate such vehicles. In addition to acid sensitivity, they benefit from conformational rigidity that is otherwise not attainable by their non-spirocyclic analogs. Herein, amphiphilic spirocyclic polyacetals are synthesized by Cu-catalyzed alkyne–azide “click” polymerization. Unlike conventional block copolymers, which often form core–shell structures, these polymers self-assemble to form core amphiphilic assemblies capable of encapsulating Nile red as a hydrophobic model drug. In vitro experiments show that while release from these materials can occur at neutral pH with preservation of their integrity, acidic pH accelerates efficient cargo release and leads to the complete degradation of assemblies. Moreover, cellular assays reveal that these materials are fully cytocompatible, interact with the plasma membrane, and can be internalized by cells, rendering them as potential candidates for cancer therapy and/or drug delivery. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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14 pages, 1968 KiB

Open AccessArticle

pH-Dependent Formation of Oriented Zinc Oxide Nanostructures in the Presence of Tannic Acid

by Nurul Akmal Che Lah, Aqilah Kamaruzaman and Sonia Trigueros

Nanomaterials 2021, 11(1), 34; https://0-doi-org.brum.beds.ac.uk/10.3390/nano11010034 - 25 Dec 2020

Cited by 5 | Viewed by 2751

Abstract

To crucially comprehend the relaying factors behind the growth mechanism of ZnO nanostructures, the needs to understand the cause of preferences in the enhancement of desired physicochemical properties are essential. The particular oriented attachment (OA) is believed to become the cause of the classical growth pattern of ZnO nanostructures which is mainly controlled by the Ostwald ripening (OR) process. In the present work, the concerns over the systematic changes in size and the morphological surface of ZnO nanostructures upon exposure to tannic acid (TA) prepared by drop-wise method turns the particles to different surface adjustment state. Here, we assessed the TA capping ability and its tendency to influence the OA process of the ZnO nanostructures. The detailed process of the growth-based TA system via transmission electron microscopy (TEM), scanning electron microscopy (SEM), and FFT autocorrelation revealed the pH effect on their physical properties which proved the transition surface properties state of the particles from rough to smooth states due to oriented attachment. For pure ZnO nanostructures, the surface is almost smooth owing to the strong bonding particles which are then changed to coarsened surface structures upon the introduction of TA. Strong surface adsorption of Zn cations and phenol ligands mediated the agglomerated nanocrystals, surprisingly with smaller nanostructures dimension. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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Review

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32 pages, 8622 KiB

Open AccessReview

Advances and Novel Perspectives on Colloids, Hydrogels, and Aerogels Based on Coordination Bonds with Biological Interest Ligands

by Noelia Maldonado and Pilar Amo-Ochoa

Nanomaterials 2021, 11(7), 1865; https://0-doi-org.brum.beds.ac.uk/10.3390/nano11071865 - 20 Jul 2021

Cited by 11 | Viewed by 3142

Abstract

This perspective article shows new advances in the synthesis of colloids, gels, and aerogels generated by combining metal ions and ligands of biological interest, such as nucleobases, nucleotides, peptides, or amino acids, among other derivatives. The characteristic dynamism of coordination bonds between metal center and biocompatible-type ligands, together with molecular recognition capability of these ligands, are crucial to form colloids and gels. These supramolecular structures are generated by forming weak van der Waals bonds such as hydrogen bonds or π–π stacking between the aromatic rings. Most gels are made up of nano-sized fibrillar networks, although their morphologies can be tuned depending on the synthetic conditions. These new materials respond to different stimuli such as pH, stirring, pressure, temperature, the presence of solvents, among others. For these reasons, they can trap and release molecules or metal ions in a controlled way allowing their application in drug delivery as antimicrobial and self-healable materials or sensors. In addition, the correct selection of the metal ion enables to build catalytic or luminescent metal–organic gels. Even recently, the use of these colloids as 3D-dimensional printable inks has been published. The elimination of the solvent trapped in the gels allows the transformation of these into metal–organic aerogels (MOAs) and metal–organic xerogels (MOXs), increasing the number of possible applications by generating new porous materials and composites useful in adsorption, conversion, and energy storage. The examples shown in this work allow us to visualize the current interest in this new type of material and their perspectives in the short-medium term. Furthermore, these investigations show that there is still a lot of work to be done, opening the door to new and interesting applications. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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31 pages, 18599 KiB

Open AccessReview

A Perspective on the Application of Covalent Organic Frameworks for Detection and Water Treatment

by Cristina Arqueros, Félix Zamora and Carmen Montoro

Nanomaterials 2021, 11(7), 1651; https://0-doi-org.brum.beds.ac.uk/10.3390/nano11071651 - 23 Jun 2021

Cited by 16 | Viewed by 4139

Abstract

Global population growth and water resource scarcity are significant social problems currently being studied by many researchers focusing on finding new materials for water treatment. The aim is to obtain quality water suitable for drinking and industrial consumption. In this sense, an emergent class of crystalline porous materials known as Covalent-Organic Frameworks (COFs) offers a wide range of possibilities since their structures can be designed on demand for specific applications. Indeed, in the last decade, many efforts have been made for their use in water treatment. This perspective article aims to overview the state-of-the-art COFs collecting the most recent results in the field for water detection of pollutants and water treatment. After the introduction, where we overview the classical design strategies on COF design and synthesis for obtaining chemically stable COFs, we summarize the different experimental methodologies used for COFs processing in the form of supported and free-standing membranes and colloids. Finally, we describe the use of COFs in processes involving the detection of pollutants in water and wastewater treatment, such as the capture of organic compounds, heavy metals, and dyes, the degradation of organic pollutants, as well as in desalination processes. Finally, we provide a perspective on the field and the potential technological use of these novel materials. Full article

(This article belongs to the Special Issue Preparation and Characterization of Nanomaterials with Multifunctional Properties)

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