Advanced Functional Nanomaterials Research Articles

Converting Chrysotile Nanotubes into Magnesium Oxide and Hydroxide Using Lanthanum Oxycarbonate Hybridization and Alkaline Treatment for Efficient Phosphate Adsorption

Magnesium oxide and hydroxide nanomaterials comprise a class of promising advanced functional metal nanomaterials whose use in environmental and material applications is increasing. Several strategies to synthesize these nanomaterials have been described but are unsustainable and uneconomic. This work reports on a processing strategy that turns natural magnesium-rich chrysotile into magnesium oxide and hydroxide nanoparticles via nanoparticle hybridization and an alkaline process while enabling La-based nanoparticles to coat the chrysotile nanotube surfaces. The adsorbent's resulting hybrid nanostructure had an outstanding capacity for phosphate uptake (135.2 mg P g-1) and enhanced regeneration performance. Furthermore, the adsorbent featured wide applicability with respect to the coexistence of competitive anions and a broad range of pH conditions, and its high-performance phosphate removal from sewage effluent was also demonstrated. Spectroscopic and microscopic analyses revealed the scavenging ability of phosphate by the La-based and Mg-based nanoparticles and the multiple capture mechanisms involved, including surface complexation and ion exchange. This proposed approach expands chrysotile's potential use as a magnesium-rich nanomaterial and harbors great promise for the removal of pollutants in a variety of real-world settings.

Construction of a Hierarchical Structure of Bimetallic Oxide Derived from Metal-Organic Frameworks.

Bimetallic oxides are a class of promising advanced functional metal nanomaterials, especially in terms of the sophisticated hierarchical structure of bimetallic oxide, which not only is in favor of enhancing their intrinsic physiochemical properties because of more accessible actives sites but also is capable of integrating the synergistic effect between two metals. Herein, we report a novel strategy to controllably construct bimetallic CuO/ZnO nanomaterials with sophisticated hierarchical structure through a pseudomorphic transformation and subsequent calcination process. The resulting unique hierarchical structure of ZnO/CuO is primarily constituted of a nanosphere and a rod grafted in a microscale cube with multidimensional size, which thus results in excellent dispersion, superior charge-transport capability, and abundant accessible active sites. Impressively, the optimized hierarchical structure product of CuO/ZnO (4:1) demonstrates an excellent glucose detection performance with a rapid response time, a wide linear range, a low detection limit, and strong antiinterference ability, realizing more advantages than commercial CuO or ZnO materials and shedding light on the positive correlation of the structure and performance. This study provides a new strategy for the controllable fabrication of the sophisticated hierarchical structure of bimetallic oxide nanomaterials.

MXene-Based Electrodes for Supercapacitor Energy Storage

MXenes, a new class of two-dimensional advanced functional nanomaterials, have been widely researched in the past decade for applications in diverse fields including clean energy and fuels production. The unique layered structures of MXenes simultaneously enhance electrolyte ion transport and provide transition metal active redox sites on the surface. These features make MXenes particularly promising for applications as high-performance electrodes for electrochemical capacitors (supercapacitors). This paper critically reviews the latest advancements in the utilization of MXenes in supercapacitor electrodes. The key structural features and other properties of MXenes that make them ideal for supercapacitor electrodes, including strategies for fabrication, performance improvement, and scalable manufacture of industry-relevant MXene films, are elaborated. Future research needs, challenges, and opportunities in this rapidly emerging area are discussed as well.

Hierarchical assemblies of polypeptoids for rational design of advanced functional nanomaterials.

Polypeptoids (poly-N-substituent glycines) are a class of highly tailorable peptidomimetic polymers. Polypeptoids have identical backbones as polypeptides (poly-C-substituent glycines), but sidechains of polypeptoids are appended to backbone nitrogen rather than α-carbon of polypeptides. As a result, peptoid backbone lacks of chirality and hydrogen bond donors. This unique structure gives polypeptoids a combined merit of both high stability as synthetic polymers and biocompatibility as biopolymers. In addition, peptoid sequences can be engineered precisely to assemble specific crystalline patterns such as spheres, fibers, ribbons, tubes, and sheets, which shows promising potentials of polypeptoids for different applications such as antimicrobials, catalysts, drug delivery, and templating inorganic materials. In this review, we summarize recent investigations into hierarchical self-assembly pathways and molecular structures of peptoid crystals that are of interest as templates for fabricating functional materials for potential biomedical, biochemical, and bioengineering applications. This review provides a summary of recent experimental and computational studies of polypeptoid assembly in solution and solid-liquid interfaces, current achievements in the field, and discusses future challenges and opportunities for the rational design of self-assembled polypeptoid nanomaterials.

Drug–zein@lipid hybrid nanoparticles: Electrospraying preparation and drug extended release application

The reasonable selection and elaborate conversion of raw materials into desired functional products represent a main topic in modern material engineering. In this study, zein (a plant protein) and lipids (extracted from egg yolk) are converted into a new type of drug–polymer@lipid hybrid nanoparticles (HNPs) via modified coaxial electrospraying. Tamoxifen citrate (TC) is used as a model anticancer drug to prepare TC–zein monolithic nanocomposites (MNCs) via traditional blended electrospraying; these MNCs are then used for comparison. Modified coaxial electrospraying is a continuous and robust process for the preparation of solid particles because of the action of unsolidifiable shell lipid solutions. HNPs have a round morphology with clear core–shell nanostructures, whereas MNCs have an indented flat morphology. Although both hold the drug in an amorphous state because of the fine compatibility of TC and zein, HNPs demonstrate a better sustained release of TC compared with MNCs in terms of retarding initial burst release (6.7 %±2.9 % vs. 37.2 %±4.3 %) and prolonged linear release period (20.47 h vs. 4.97 h for releasing 90 % of the loaded drug). Mechanisms by which the shell’s lipid layer adjusts the release behavior of TC molecules are proposed. The present protocol based on coaxial electrospraying shows a new strategy of combining edible protein and lipids to fabricate advanced functional nanomaterials.

Combination of structure-performance and shape-performance relationships for better biphasic release in electrospun Janus fibers

In nature, the combination of composition, structure, and shape determines the matter's functional performance to a large extent. Inspired by which, two electrospun Janus nanofiber formulations were created using side-by-side electrospinning in this work. Tamoxifen citrate (TAM) was used as a model drug and ethyl cellulose (EC) and polyvinylpyrrolidone K60 (PVP) as the polymer carrier matrices. The fibers have linear cylindrical morphologies and distinct Janus structures by scanning electron microscopy. One side of the fibers took a round shape, while the other was crescent-shaped. The drug was present in both polymer matrices in the form of amorphous solid dispersions, owing to strong intermolecular interactions between drug and polymer. In vitro dissolution tests demonstrated that both sets of fibers could provide biphasic drug release due to the difference in solubility of PVP and EC. The different shape of TAM-EC and TAM-PVP side of the Janus structure resulted in a considerable variation in the drug release profiles. The Janus structure with crescent TAM-PVP side and round TAM-EC side gave a more rapid burst release in the first phase of release, and slower sustained release in the second phase. This work thus reports a new strategy for systematically developing advanced functional nanomaterials based on both shape- and structure-performance relationships.

Atmospheric-pressure plasma seawater desalination: Clean energy, agriculture, and resource recovery nexus for a blue planet

Water connects every aspect of life. Only 4% of the world's water is fresh water, as most water sources have different degrees of salinity. As a result, billions of people face water scarcity, which is a global challenge. Desalination technologies that separate fresh water from solvated salt ions in saline water are attracting major attention. However, conventional desalination processes including thermally and pressure driven processes are highly energy intensive. To address this issue we demonstrate that the atmospheric-pressure plasma (APP) treatment of saline water can be a new potential alternative low-energy and green desalination route. Valuable salts are recovered by direct salt crystal precipitation within a short plasma processing time. During desalination and salt precipitation, plasma activated desalinated water (PADW) is generated and can be used for clean energy processes such as water electrolysis and sustainable agriculture by enhanced plant seed germination. In addition, functional nanomaterials can be extracted from the precipitated salt. The PADW exhibited a low salinity of 5.6 mS/cm with a low pH value of 2.1. The unique intrinsic PADW chemistries enabled electrochemical water splitting for both the hydrogen evolution reaction (HER) at a Pt electrode and the oxygen evolution reaction (OER) at a RuO2 electrode. Moreover, the feasibility of using PADW in sustainable agriculture was demonstrated by enhancing mungbean seed germination using tap water mixed with PADW. At optimum mix concentration, both seed germination rates and germination percentages increased. Finally, we demonstrated the feasibility of synthesizing high-value 2D nanomaterials exemplified by Mg(OH)2 nanosheets via a single step thermal process using the salt precipitated from the seawater by the plasma process. Combined with straightforward use of renewable electricity to generate APPs, this study reveals the plasma potential for sustainable recovery of clean water, clean energy applications, sustainable agriculture, and manufacturing of advanced functional nanomaterials – all from the greatest treasure of our blue planet – seawater.

Electrospun Janus nanofibers loaded with a drug and inorganic nanoparticles as an effective antibacterial wound dressing.

The most important property of a wound dressing is its anti-bacteria performance. Although electrospun nanofibers are frequently demonstrated to be potent candidates as wound dressings, no Janus fibers have been explored for this popular application. In this study, a Janus wound dressing composed of polyvinylpyrrolidone (PVP) and ethyl cellulose (EC) polymer matrices was prepared via a side-by-side electrospinning process, in which ciprofloxacin (CIP) and silver nanoparticles (AgNPs) were loaded in the two sides. A homemade acentric spinneret was exploited to maintain a continuous preparation process. Scanning and transmission electron microscope results demonstrated that the Janus fibers had a uniform and cylindrical morphology with a clear Janus structure, and AgNPs distributed in one side. X-ray diffraction patterns suggested that drug was present in the fibers in an amorphous state owing to rapid drying and its good compatibility with PVP, which was verified by infrared spectroscopy. In vitro tests showed that over 90% of CIP was released within the first 30min, ensuring a strong antibacterial effect at the initial stages of wound healing. The Janus fibers were demonstrated to have good bactericidal activity against the growth of both Gram-positive S. aureus and Gram-negative E. coli. The PVP-CIP/EC-AgNPs Janus fibers could thus be a promising candidate for effective wound dressings. This work paves a new way for creating Janus structure-based advanced functional nanomaterials.

Multifluid electrospinning for the generation of complex nanostructures.

New nanostructure means new nanotechnology and nanoscience. The need of complex nanostructure-based advanced functional nanomaterials has promoted the appearance of several kinds of multifluid electrospinning processes, such as tri-axial electrospinning, quad-fluid coaxial electrospinning, tri-fluid side-by-side electrospinning, and coaxial electrospinning with a side-by-side core. These multifluid processes can greatly expand the capability of electrospinning in generating new types of nanostructures with different organization manner of the inner parts, and from both spinnable and unspinnable working fluids. The key elements for conducting a multifluid electrospinning lie in a well-designed spinneret, compatibility of the working fluids, and special operational parameters. The complex nanostructures can be created through direct electrospinning of multiple fluids, through after-treatment of the electrospun products, and through ingenious design of the components, compositions and their spatial distributions as well. This article provides a simple review on the most recent publications about the multifluid electrospinning processes and the corresponding complex nanostructures. This article is characterized under: Therapeutic Approaches and Drug Discovery > Emerging Technologies Implantable Materials and Surgical Technologies > Nanomaterials and Implants.

A facile synthesis of ruthenium/reduced graphene oxide nanocomposite for effective electrochemical applications

The synthesis of advanced functional nanomaterials for electrochemical applications, such as water splitting, dye-sensitized solar cells (DSCs), and supercapacitor has been the topic of interest in recent years. This work presents the synthesis of ruthenium (Ru)/reduced graphene oxide (RGO) nanocomposite by using a facile and scalable liquid plasma-assisted method and its application as an electrode material in electrochemical applications for supercapacitor and triiodide reduction at counter electrodes (CEs) of DSCs. As the results, Ru nanoparticles have a size in the range of 4–10 nm that were homogenously distributed on the surface of the RGO layer. Electrochemical measurements demonstrated that the synthesized material is suitable for supercapacitor applications, whereas the capacitance is approximately 136.7 F·g−1 at a scan rate of 20 mV·s−1. The developed materials are applied in CEs of DSCs. We found that the efficiency of 6.78% for DSCs with CE fabricated by Ru/RGO which is higher than that of 6.20% for a cell assembled with Pt electrode.

Cr(III) Adsorption by Cluster Formation on Boehmite Nanoplates in Highly Alkaline Solution.

The development of advanced functional nanomaterials for selective adsorption in complex chemical environments requires partner studies of binding mechanisms. Motivated by observations of selective Cr(III) adsorption on boehmite nanoplates (γ-AlOOH) in highly caustic multicomponent solutions of nuclear tank waste, here we unravel the adsorption mechanism in molecular detail. We examined Cr(III) adsorption to synthetic boehmite nanoplates in sodium hydroxide solutions up to 3 M, using a combination of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS), scanning/transmission electron microscopy (S/TEM), electron energy loss spectroscopy (EELS), high-resolution atomic force microscopy (HR-AFM), time-of-fight secondary ion mass spectrometry (ToF-SIMS), Cr K-edge X-ray absorption near edge structure (XANES)/extended X-ray absorption fine structure (EXAFS), and electron paramagnetic resonance (EPR). Adsorption isotherms and kinetics were successfully fit to Langmuir and pseudo-second-order kinetic models, respectively, consistent with monotonic uptake of Cr(OH)4- monomers until saturation coverage of approximately half the aluminum surface site density. High resolution AFM revealed monolayer cluster self-assembly on the (010) basal surfaces with increasing Cr(III) loading, possessing a structural motif similar to guyanaite (β-CrOOH), stabilized by corner-sharing Cr-O-Cr bonds and attached to the surface with edge-sharing Cr-O-Al bonds. The selective uptake appears related to short-range surface templating effects, with bridging metal connections likely enabled by hydroxyl anion ligand exchange reactions at the surface. Such a cluster formation mechanism, which stops short of more laterally extensive heteroepitaxy, could be a metal uptake discrimination mechanism more prevalent than currently recognized.

Convenient design of porous and heteroatom self-doped carbons for CO2 capture

Porous and heteroatoms self-doped carbon (PHCs) materials are synthesized for the first time by employing carbonization of casein with ZnCl2 at a temperature of 800 °C. The synthesis involves a one-step solid state carbonization cum activation to synthesize PHCs with high specific surface areas and surface functionalization with nitrogen and oxygen. The textural properties of PHCs including specific surface area, pore volume and pore size can easily be controlled by adjusting the activation amounts of ZnCl2. The optimized material (PHC4) is synthesized with ZnCl2/casein impregnation ratio of 4 and it shows a high specific surface area (1080 m2 g�1) and an appreciable amount of heteroatoms, nitrogen (4.4) and oxygen (4.7). PHC4 exhibits a high CO2 adsorption capacity at 0 °C/1 bar (3.5 mmol g�1) and 0 °C/30 bar (15.8 mmol g�1). Additionally, the presence of heteroatoms on the surface results in enhancement of interactions between CO2 and the adsorbents which are evident from a high value of isosteric heat of adsorption (�35 kJ mol�1) calculated using Clausius Clapeyron's equation. The reported activation synthesis strategy could be explored further to devise advanced functional nanomaterials for specific adsorption applications. © 2019

Metal chelate monomers based on nickel(II) cinnamate and chelating N-heterocycles as precursors of nanostructured materials

Metal chelate monomers (MCMs) have been widely used as precursors for the production of advanced functional polymers and nanomaterials. In this articel, new metal chelate monomers based on nickel(II) cinnamate (cinn) and various chelating N-heterocycles, [Ni(cinn)2(bpy)(C2H5OH)] and [Ni(cinn)2(phen)(C2H5OH)2] (bpy = 2,2′-bipyridine and phen = 1,10-phenanthroline), were first synthesized and characterized. A detailed analysis of the main stages and features of the kinetics of thermolysis of MCMs was carried out. Metal-polymer nanocomposites with a core-shell structure containing metal nanoparticles evenly distributed in a stabilizing nitrogen-containing polymer matrix were obtained by thermolysis at 300 °C. Thermolysis at 450 °C resulted in pure nickel oxide nanoparticles. The nature of the ligand has been shown to affect the structure and size of the product obtained. The tribological characteristics of nanoparticles as additives to lubricating oils were studied using the pin-on-disc tribometer. At the optimum concentration of nanoparticles, the coefficient of friction is the smallest, and an increase in the concentration above the optimum level leads to an increase in the coefficient of friction.

Advanced on-site glucose sensing platform based on a new architecture of free-standing hollow Cu(OH)2 nanotubes decorated with CoNi-LDH nanosheets on graphite screen-printed electrode.

The planned design of nanocomposites combined with manageable production processes, which can offer controllability over the nanomaterial structure, promises the practical applications of functional nanomaterials. Hollow core-shell nanostructure architectures represent an emerging category of advanced functional nanomaterials, whose benefits derived from their notable properties may be hampered by complicated construction processes, especially in the sensing domain. In this regard, we designed a highly porous three-dimensional array of hierarchical hetero Cu(OH)2@CoNi-LDH core-shell nanotubes via a quick, very simple, green, and highly controllable three-step in situ method; they were directly grown on a glassy carbon electrode to fabricate an enzyme-free glucose sensor. By virtue of an open structure containing a hollow conductive core and a highly porous catalytic active shell, which were both synthesized by the in situ method, hierarchical self-standing core-shell nanotubes were obtained. They provided an enlarged active surface area, highly accessible catalytic sites, faster electron transfer, effortless electrolyte ion diffusion pathways, and structural stability, thus leading to improved electrocatalytic performances and durability towards glucose electro-oxidation; this was reflected by the fast sensitive responses of the as-prepared sensor towards glucose and comparable results with the automatic biochemistry analyzer used in hospitals in real sample analysis. Moreover, the commercialization capability of the proposed sensor was evaluated analogously by directly grown hierarchical Cu(OH)2@CoNi-LDH core-shell nanotubes on graphite screen-printed exposable electrodes through a 3-step in situ method. Cu(OH)2@CoNi-LDH NS-NTs/GSPE showed accurate responses towards glucose, lack of any fouling effect of the electrocatalyst layer over a wide range of glucose concentrations and comparable results with that of a commercial glucometer in real sample analysis, which revealed high sensitivity, selectivity, and durability of the low-cost on-site sensor as well as excellent versatility of its fabrication method. Thus, the self-supporting, cost-affordable, facile, and fast electrode fabrication procedure with versatility and meticulous structural controllability presented in this research provides a new architecture for the advancement of high-performance electrochemical sensors and miniaturized detection devices.

All-Poly(ionic liquid) Membrane-Derived Porous Carbon Membranes: Scalable Synthesis and Application for Photothermal Conversion in Seawater Desalination.

Herein, we introduce a straightforward, scalable, and technologically relevant strategy to manufacture charged porous polymer membranes (CPMs) in a controllable manner. The pore sizes and porous architectures of CPMs are well-controlled by rational choice of anions in poly(ionic liquid)s (PILs). Continuously, heteroatom-doped hierarchically porous carbon membrane (HCMs) can be readily fabricated via morphology-maintaining carbonization of as-prepared CPMs. These HCMs, as photothermal membranes, exhibited excellent performance for solar seawater desalination, representing a promising strategy to construct advanced functional nanomaterials for portable water production technologies.

Cooperation of Amphiphilicity and Smectic Order in Regulating the Self-Assembly of Cholesterol-Functionalized Brush-Like Block Copolymers.

Nanoparticle morphology significantly affects the application of nanometer-scale materials. Understanding nanoparticle formation mechanisms and directing morphological control in nanoparticle self-assembly processes have received wide attention. Herein, a series of brush-like amphiphilic liquid crystalline block copolymers, PChEMA m- b-POEGMA n, containing cholesteryl mesogens with different hydrophobic/hydrophilic block ratios were designed and synthesized. The self-assembly behaviors of the resulting PChEMA m- b-POEGMA n block copolymers in different solvents (tetrahydrofuran/H2O, 1,4-dioxane/H2O, and N, N-dimethylformamide) were investigated in detail. Desirable micellar aggregates with well-organized architectures, including short cylindrical micelles, nanofibers, fringed platelets, and ellipsoidal vesicles with smectic micellar cores, were observed in 1,4-dioxane/H2O with an increasing hydrophobic block ratio. Although both amphiphilicity and smectic order governed the self-assembly, these two factors were differently balanced in the different solvents. This unique supramolecular system provides a new strategy for the design of advanced functional nanomaterials with tunable morphologies.

Modification of electrospun PVA/PAA scaffolds by cold atmospheric plasma: alignment, antibacterial activity, and biocompatibility

The ongoing search for better antibacterial wound care dressings has led to the design and fabrication of advanced functional nanomaterials. Taking advantage of electrospinning and cold atmospheric plasma (CAP), free-standing nanofibrous scaffolds are promising for use in novel biomedical applications. Random and aligned polyvinyl alcohol (PVA)/polyacrylic acid (PAA) nanofiber scaffolds are fabricated by electrospinning and treated with CAP. In this study, we investigate the effects of CAP treatment on alignment, hydrophilicity, antibacterial activity, and biocompatibility in determining the surface properties of the nanofibrous scaffolds. The results of vibrational polarization spectroscopy analysis indicate that CAP treatment changes the degree of alignment of the nanofibers. Furthermore, both random and aligned CAP-treated nanofibrous scaffolds show significant antibacterial activity against the E. coli strain. The results of an in vitro scratch assay reveal that CAP treatment of PVA/PAA nanofibers has no toxic effect.

Wrapping Nanocellulose Nets around Graphene Oxide Sheets

AbstractConstructing advanced functional nanomaterials with pre‐designed organized morphologies from low‐dimension synthetic and biological components is challenging. Herein, we report an efficient and universal amphiphilicity‐driven assembly strategy to construct “hairy” flexible hybrid nanosheets with a 1D cellulose nanofibers (CNFs) net conformally wrapped around 2D graphene oxide (GO) monolayers. This interface‐driven bio‐synthetic assembly is facilitated by tailoring the surface chemistry of flexible GO sheets, resulting in individual sheets tightly surrounded by dense conformal nanocellulose network. The mechanical stability of the products far exceeds the compressive instability limits of both individual components. Additionally, the CNF network significantly enhances the wetting ability of initial hydrophobic reduced GO nanosheets, allowing fast water transport combined with high filtration efficiency.

Wrapping Nanocellulose Nets around Graphene Oxide Sheets.

Constructing advanced functional nanomaterials with pre-designed organized morphologies from low-dimension synthetic and biological components is challenging. Herein, we report an efficient and universal amphiphilicity-driven assembly strategy to construct "hairy" flexible hybrid nanosheets with a 1D cellulose nanofibers (CNFs) net conformally wrapped around 2D graphene oxide (GO) monolayers. This interface-driven bio-synthetic assembly is facilitated by tailoring the surface chemistry of flexible GO sheets, resulting in individual sheets tightly surrounded by dense conformal nanocellulose network. The mechanical stability of the products far exceeds the compressive instability limits of both individual components. Additionally, the CNF network significantly enhances the wetting ability of initial hydrophobic reduced GO nanosheets, allowing fast water transport combined with high filtration efficiency.

Enzyme-functionalized DNA nanostructures as tools for organizing and controlling enzymatic reactions

Abstract