Controlling the Magnetic Responsiveness of Cellulose Nanofiber Particles Embedded with Iron Oxide Nanoparticles.

2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofiber (TOCN) particles, an innovative biobased material derived from wood biomass, have garnered significant interest, particularly in the biomedical field, for their distinctive properties as biocompatible particle adsorbents. However, their microscopic size complicates their separation in liquid media, thereby impeding their application in various domains. In this study, superparamagnetic magnetite nanoparticles (NPs), specifically iron oxide Fe3O4 NPs with an average size of 15 nm, were used to enhance the collection efficiency of TOCN-Fe3O4 composite particles synthesized through spray drying. These composite particles exhibited a remarkable ζ-potential (approximately -50 mV), indicating their high stability in water, as well as impressive magnetization properties (up to 47 emu/g), and rapid magnetic responsiveness within 60 s in water (3 wt % Fe3O4 to TOCN, 1 T magnet). Furthermore, the influence of Fe3O4 NP concentrations on the measurement of the speed of magnetic separation was quantitatively discussed. Additionally, the binding affinity of the synthesized particles for proteins was assessed on a streptavidin-biotin binding system, offering crucial insights into their binding capabilities with specific proteins and underscoring their significant potential as functionalized biomedical materials.

Controllable Synthesis of Porous and Hollow Nanostructured Catalyst Particles and Their Soot Oxidation.

The introduction of macroporous structures into three-way catalysts (TWCs) through polymer template-assisted spray drying has attracted attention because of its enhanced gas diffusion and catalytic performance. However, the surface charge effect of polymeric template components has not been investigated to control the structure of the TWC particles during synthesis. Thus, this study investigated the effect of template surface charges on the self-assembly behavior of TWC nanoparticles (NPs) during drying. The self-assembly of TWC NPs and polymer particles with different charges produced a hollow structure, whereas using the same charges generated a porous one. Consequently, the mechanism of particle self-assembly during drying and final structure particle formation is proposed in this study. Here, porous TWC particles demonstrated a faster oxidation of soot particles than that of hollow-structured particles. This occurred as a result of the larger contact area between the catalyst surface and the solid reactant. Our findings propose a fundamental self-assembly mechanism for the formation of different TWC structures, thereby enhancing soot oxidation performance using macroporous structures.

Macropore-Size Engineering toward Enhancing the Catalytic Performance of CO Oxidation over Three-Way Catalyst Particles.

In recent years, transportation-related air pollution has escalated into a global concern, necessitating the development of a three-way catalyst (TWC) technology to address harmful emissions. However, the efficiency of TWC's performance in mitigating these emissions has been hindered because of limited mass transfer efficiency within their structures. Thus, this study attempted to overcome the existing issue by synthesizing a series of macroporous TWC particles exhibiting various macropore sizes via a template-assisted spray process, aiming to achieve optimal mass transfer efficiency and catalytic performance. The synthesis incorporated various template particles (size of 67-381 nm) to obtain various macroporous structures. Thereafter, these macroporous particles were assessed for their carbon monoxide (CO) oxidation performance, revealing a substantial influence of the macropore size on the catalytic performance of TWC structures. Interestingly, among the investigated samples, those containing the smallest and largest macropores demonstrated the highest CO oxidation performances. Based on these results, a plausible reactant diffusion mechanism was proposed to explain the effect of the macropore size on the diffusion efficiency within the macroporous structures. This work may have significant implications in optimizing the macroporous structure to enhance catalytic performance in the gas purification process.

Multifunctional, Hybrid Materials Design via Spray-Drying: Much more than Just Drying.

Spray-drying is a popular and well-known "drying tool" for engineers. This perspective highlights that, beyond this application, spray-drying is a very interesting and powerful tool for materials chemists to enable the design of multifunctional and hybrid materials. Upon spray-drying, the confined space of a liquid droplet is narrowed down, and its ingredients are forced together upon "falling dry." As  detailed in this article, this enables the following material formation strategies either individually or even in combination: nanoparticles and/or molecules can be assembled; precipitation reactions as well as chemical syntheses can be performed; and templated materials can be designed. Beyond this, fragile moieties can be processed, or "precursor materials" be prepared. Post-treatment of spray-dried objects eventually enables the next level in the design of complex materials. Using spray-drying to design (particulate) materials comes with many advantages-but also with many challenges-all of which are outlined here. It is believed that multifunctional, hybrid materials, made via spray-drying, enable very unique property combinations that are particularly highly promising in myriad applications-of which catalysis, diagnostics, purification, storage, and information are highlighted.

Synthesis of Submicron-Sized Spherical Silica-Coated Iron Nickel Particles with Adjustable Shell Thickness via Swirler Connector-Assisted Spray Pyrolysis.

Silica-coated iron nickel (FeNi@SiO2) particles have attracted significant attention because of their potential applications in electronic devices. In this work, submicron-sized spherical FeNi@SiO2 particles with precisely controllable shell thickness were successfully synthesized for the first time using a swirler connector-assisted spray pyrolysis system, comprising a preheater, specific connector, and main heater. The results indicated that the thickness of the SiO2 shell can be tuned from 3 to 23 nm by adjusting the parameter conditions (i.e., preheater temperature, SiO2 supplied amount). Furthermore, our fabrication method consistently yielded a high coating ratio of more than 94%, indicating an excellent quality of the synthesized particles. Especially, to gain an in-depth understanding of the particle formation process of the FeNi@SiO2 particles, a plausible mechanism was also investigated. These findings highlight the importance of controlling the preheater and SiO2 supplied amount to obtain FeNi@SiO2 particles with desirable morphology and high coating quality.

Novel strategy for high-performance supercapacitors through the polyvinylpyrrolidone (PVP)-assisted in situ growth of FeS2.

Iron disulfide or pyrite (FeS2) has emerged as a promising transition metal sulfide-based supercapacitor owing to its abundance and superb electrochemical properties. However, FeS2 still faces major hurdles in realizing its full potential, such as a low energy density and poor conductivity. In this study, we report a high-performance FeS2 supercapacitor synthesized by a direct one-step process with the help of polyvinylpyrrolidone (PVP). The incorporation of PVP on the active materials prevented dendritic expansion and acted as a binding for solving the current FeS2 limitations, while facilitating a one-step synthesis process. Additionally, PVP could enhance the electrochemical performance by enabling faster ion movement. An FeS2/PVP nanocomposite was successfully synthesized, and used in an asymmetric supercapacitor, demonstrating a high specific capacity of 735 F g-1 (at 2 A g-1) and a high energy density of 69.74 W h kg-1 (at 911 W kg-1). The superior electrochemical properties of FeS2/PVP were enabled by the lower charge-carrier resistance and better surface passivation by PVP, as demonstrated by both electrochemical experiments and first-principles calculations. The high-performance supercapacitor of FeS2 presented in this study synthesized in situ by an efficient method provides a new insight into novel supercapacitor electrodes.

Rapid Indomethacin Release from Porous Pectin Particles as a Colon-Targeted Drug Delivery System.

The conventional pectin delivery systems in the colon are often impaired by a slow release rate. Nanostructured particles, especially porous ones, have gained popularity as drug delivery systems owing to their high mass transfer efficiency. In this research, porous pectin particles were synthesized as drug carriers (using indomethacin as a model drug) via template-assisted spray drying. Specific surface areas of the porous pectin particles have been improved by up to 203 m2 g-1 compared with nonporous particles (1 m2 g-1). The porous structure shortened the diffusion path and improved the release rate of drug molecules. Additionally, the predominant drug release mechanism from porous pectin particles is Fickian diffusion, which is different from the combination of erosion and diffusion mechanism observed for nonporous particles. As a result, these porous drug-loaded pectin particles demonstrated rapid drug release rates of up to three times faster than nonporous particles. Control of the release rate could be achieved by changing the porous structure of the particles. This strategy is an efficient means to synthesize porous particles allowing rapid drug release into the colonic target.

Designing the Macroporous Structure of Three-Way Catalyst Particles: The Influence of Template Concentration on Framework Thickness and Mass Transfer.

Mass transfer is an essential process that can extend the performance and utilization of nanoporous materials in various applications. Therefore, improving mass transfer in nanoporous materials has always attracted much interest, and macroporous structures are currently being studied to enhance mass transfer performance. The introduction of macroporous structures into three-way catalysts (TWC), which are widely utilized to control the emission of polluted gases from vehicles, provides the potential to enhance their mass transfer property and catalytic performance. However, the formation mechanism of macroporous TWC particles has not yet been investigated. On the other hand, the influence of the framework thickness of the macroporous structure on the mass transfer enhancement is still unclear. Therefore, this report investigates the particle formation and framework thickness of the macroporous TWC particles synthesized using the template-assisted aerosol process. The formation of macroporous TWC particles was precisely controlled and investigated by altering the size and concentration of the template particles. The template concentration played a crucial role in maintaining the macroporous structure and controlling the framework thickness between the macropores. Based on these results, a theoretical calculation showing the influence of template concentration on the particle morphology and framework thickness was developed. The final results showed that increasing the template concentration can positively affect the nanoporous material's framework thickness reduction and mass transfer coefficient improvement.

Tuning of water resistance and protein adsorption capacity of porous cellulose nanofiber particles prepared by spray drying with cross-linking reaction.

Porous particles composed of 2,2,6,6-tetramethylpiperidinyl-1-oxyl-oxidized cellulose nanofiber (TOCN) as building block, i.e., porous TOCN particles, are attracting attention due to their environmental friendliness, superior properties, such as easy handling, large surface area, and high adsorption capacity. However, the instability of TOCNs in aqueous environments limits their applications. An effective solution to improve water resistance of TOCN particles is to reduce the hydrophilicity of TOCNs by forming chemical bonds with a cross-linker. In this study, Carbodilite, a common, easy-to-use, commercially available cross-linker with carbodiimide groups, was used to investigate a chemical cross-linking strategy for porous TOCN particles prepared by spray drying. The water resistance of cross-linked TOCN particles was evaluated through morphological observation by SEM images. The presence of polycarbodiimide significantly increased water resistance of cross-linked TOCN particles up to 24 h. This study demonstrates the trade-off between water resistance and adsorption efficiency according to cross-linker concentrations. These data are useful for interface science of TOCNs in liquids, assisting in controlling specific properties of porous TOCN particles for particular applications in adsorption and separation.

Correction: Solid-state nitrogen-doped carbon nanoparticles with tunable emission prepared by a microwave-assisted method.

[This corrects the article DOI: 10.1039/D1RA07290K.].

Enhanced Protein Adsorption Capacity of Macroporous Pectin Particles with High Specific Surface Area and an Interconnected Pore Network.

There has been much interest in developing protein adsorbents using nanostructured particles, which can be engineered porous materials with fine control of the surface and pore structures. A significant challenge in designing porous adsorbents is the high percentage of available binding sites in the pores owing to their large surface areas and interconnected pore networks. In this study, continuing the idea of using porous materials derived from natural polymers toward the goal of sustainable development, porous pectin particles are reported. The template-assisted spray drying method using calcium carbonate (CaCO3) as a template for pore formation was applied to prepare porous pectin particles. The specific surface area was controlled from 177.0 to 222.3 m2 g-1 by adjusting the CaCO3 concentration. In addition, the effects of a macroporous structure, the specific surface area, and an interconnected pore network on the protein (lysozyme) adsorption capacity and adsorption mechanism were investigated. All porous pectin particles performed rapid adsorption (∼65% total capacity within 5 min) and high adsorption capacity, increasing from 1543 to the highest value of 2621 mg g-1. The results are attributed to the high percentage of available binding sites located in the macropores owing to their large surface areas and interconnected pore networks. The macroporous particles obtained in this study showed a higher adsorption capacity (2621 mg g-1) for lysozyme than other adsorbents. Moreover, the rapid uptake and high performance of this material show its potential as an advanced adsorbent for various macromolecules in the food and pharmaceutical fields.

A Sustainable Approach for Preparing Porous Carbon Spheres Derived from Kraft Lignin and Sodium Hydroxide as Highly Packed Thin Film Electrode Materials.

A green synthetic strategy to design biomass-derived porous carbon electrode materials with precisely tailored structure and morphology has always been a challenging goal because these materials can fulfill the demands of next-generation supercapacitors and other electrochemical devices. Potassium hydroxide (KOH) is extensively utilized as an activator since it can produce porous carbon with high specific surface area and well-developed porous channels. The exploitation of sodium hydroxide (NaOH) as an activating agent is less referenced in the literature, although it offers some advantages over KOH in terms of low cost, less corrosiveness, and simple handling procedure, all of which are appealing particularly from an industrial viewpoint. The motivation for this present study is to fabricate porous carbon spheres in a sustainable manner via a spray drying approach followed by a carbonization process, using Kraft lignin as the carbon precursor and NaOH as an alternative activation agent instead of the high-cost and high-corrosive KOH for the first time. The structure of carbon particles can be accurately transitioned from a compact to hollow structure, and the surface textural properties can be easily tuned by altering the NaOH concentration. The obtained porous carbon spheres were applied as highly packed thin film electrode materials for supercapacitor devices. The specific capacitance value of porous carbon spheres with a highly compact structure (high packing density) is 66.5 F g-1, which is higher than that of commercial activated carbon and other biomass-derived carbon. This work provides a green processing for producing low-cost and environment-friendly porous carbon spheres from abundant Kraft lignin and important insight for selecting NaOH as an activator to tailor the morphology and structure, which represents an economical and sustainable approach for energy storage devices.

Synthesis of High Specific Surface Area Macroporous Pectin Particles by Template-Assisted Spray Drying.

Many types of porous particles containing inorganic and organic substances, such as carbon, metals, metal oxides, inorganic-organic hybrids, and polymers, have been developed. However, natural polymer-derived particles are relatively rare. To our knowledge, this report describes the first synthetic method for obtaining meso-/macroporous particles made from pectin, which is a natural polymer with a wide range of biological activities suitable for active substance support applications. These porous particles were prepared using a template-assisted spray-drying method, followed by a chemical etching process. An organic template [i.e., poly(methyl methacrylate) (PMMA)] or an inorganic template [i.e., calcium carbonate (CaCO3)] was used to evaluate the resulting formation of macroporous structures in the pectin particles. Furthermore, the concentration of the templates in the precursor solution was varied to better understand the mechanism of porous pectin particle formation. The results showed that the final porous particles maintained the characteristic properties of pectin. The differences between the two templates resulted in two distinct types of porous particles that differed in their particle morphologies (i.e., spherical or wrinkled), particle sizes (ranging from 3 to 8 µm), pore sizes (ranging from 80 to 350 nm), and pore volume (ranging from 0.024 to 1.40 cm3 g-1). Especially, the porous pectin particles using the CaCO3 template have a significantly high specific surface area of 171.2 m2 g-1, which is 114 times higher than that of nonporous pectin particles. These data demonstrated the potential for using PMMA and CaCO3 templates to control and design desired porous materials.

Controllable synthesis of spherical carbon particles transition from dense to hollow structure derived from Kraft lignin.

The tailored synthesis of carbon particles with controllable shapes and structures from biomass as a raw material would be highly beneficial to meet the demands of various applications of carbon materials from the viewpoint of sustainable development goals. In this work, the spherical carbon particles were successfully synthesized through a spray drying method followed by the carbonization process, using Kraft lignin as the carbon source and potassium hydroxide (KOH) as the activation agent. As the results, the proposed method successfully controlled the shape and structure of the carbon particles from dense to hollow by adjusting the KOH concentration. Especially, this study represents the first demonstration that KOH plays a crucial role in the formation of particles with good sphericity and dense structures. In addition, to obtain an in-depth understanding of the particle formation of carbon particles, a possible mechanism is also investigated in this article. The resulting spherical carbon particles exhibited dense structures with a specific surface area (1233 m2g-1) and tap density (1.46 g cm-3) superior to those of irregular shape carbon particles.

Effect of H2SO4/H2O2 pre-treatment on electrochemical properties of exfoliated graphite prepared by an electro-exfoliation method.

The effect of pre-treating graphite sheets in a H2SO4/H2O2 solution before electro-exfoliation is reported. It was revealed that the volume fraction of H2SO4 to H2O2 during pre-treatment could control the degree of exfoliation of the resulting exfoliated graphite (EG). X-ray diffraction (XRD), Raman, and Fourier transform infrared (FTIR) spectroscopy analyses have suggested that EG produced by first pre-treating the graphite sheet in H2SO4/H2O2 solution with the H2SO4 : H2O2 volume fraction of 95 : 5 demonstrates the highest exfoliation degree. This sample also demonstrated excellent electrochemical properties with good electrical conductivity (36.22 S cm-1) and relatively low charge transfer resistance (R ct) of 21.35 Ω. This sample also showed the highest specific capacitance of all samples, i.e., 71.95 F g-1 at 1 mV s-1 when measured at a voltage range of -0.9 to 0 V. Further measurement at an extended potential window down to -1.4 V revealed the superior specific capacitance value of 150.69 F g-1. The superior morphology characteristics and the excellent electrical properties of the obtained EG are several reasons behind its exceptional properties. The pre-treatment of graphite sheets in H2SO4/H2O2 solution allegedly leads to easier and faster exfoliation. The faster exfoliation is allegedly able to prevent massive oxidation, which frequently induces the formation of graphite/graphene oxide (GO) in a prolonged process. However, too large H2O2 volume fraction involved during pre-treatment seems to cause excessive expansion and frail structure of the graphite sheets, which leads to an early breakdown of the structure during electrochemical exfoliation and prohibits layer by layer exfoliation.

Spherical submicron YAG:Ce particles with controllable particle outer diameters and crystallite sizes and their photoluminescence properties.

The purpose of this study was to demonstrate the preparation of spherical submicron YAG:Ce particles with controllable particle outer diameters and crystallite sizes and their photoluminescence (PL) properties, which were produced using a flame-assisted spray-pyrolysis method followed by the annealing process. The correlation of particle outer diameter, crystallite size, and PL performance of the prepared particles was also investigated. Experimental results showed that the increases in the particle outer diameters have an impact on the obtainment of higher PL performance. Large particle outer diameters permitted the crystallites to grow more, whereas this is in contrast to the condition for small particle outer diameter having limitations in crystallite growth. This study also found that too large outer diameter (>557 nm) was not effective since crystallites cannot grow anymore and it permits possible scattering problems. This study provides significant information for optimizing synthesis parameters for controlling particle outer diameters and crystallite sizes, which could be relevant to other functional properties, especially for lens, solar cell, and LED applications.

Solid-state nitrogen-doped carbon nanoparticles with tunable emission prepared by a microwave-assisted method.

Tunable emissive solid-state carbon nanoparticles (CNPs) have been successfully synthesized by a facile synthesis through microwave irradiation. Modulating microwave interaction with the sample to generate abrupt localized heating is a long-term challenge to tailor the photoluminescence properties of CNPs. This study systematically revealed that the sample temperature through microwave irradiation plays a crucial role in controlling the photoluminescence properties over other reaction conditions, such as irradiation time and microwave duty cycle. When the sample temperature reached 155 °C in less than three minutes, the CNP sample exhibited a green-yellowish emission with the highest quantum yield (QY) of 14.6%. Time-dependent density functional theory (TD-DFT) study revealed that the tunable photoluminescence properties of the CNPs can possibly be ascribed to their nitrogen concentrations, which were dictated by the sample temperature during irradiation. This study opens up a promising route for the well-controlled synthesis of luminescent CNPs through microwave irradiation.

Effective Factor on Catalysis of Niobium Oxide for Magnesium.

Magnesium is a promising hydrogen storage material but requires an efficient catalyst to enhance the sluggish kinetics of its hydrogen desorption/absorption reactions. Niobium catalysts have been shown to accomplish this, but the effective factors for catalysis on hydrogen desorption/absorption of Mg are not well understood. In order to investigate these aspects, various types of Nb oxides were synthesized and mixed with Mg, and their catalytic properties were investigated. The spray pyrolysis synthesis of Nb oxides at different temperatures produced homogeneous spherical particles with different degrees of crystallinity, while Nb oxide particles synthesized by simple calcination of ammonium niobium oxalate were nonuniform. These Nb oxides show significant catalytic activities for the hydrogen desorption/absorption of Mg, with amorphous oxides being more effective catalyst precursors than crystalline precursors. Metastable, amorphous Nb oxide is more easily converted to the reduced state, which is the catalytically active state for the reactions. In addition, Nb in the deactivated sample is in the oxidized state compared with the initially activated sample, and the catalytically active (reduced) state is recovered by reactions with hydrogen. Based on these findings, it is concluded that the chemical state of Nb is an important factor in catalyzing the desorption/absorption of hydrogen by Mg, and the catalytically active state can be preserved without further treatments.

Enhanced magnetic performance of aligned wires assembled from nanoparticles: from nanoscale to macroscale.

Magnetic wires in highly dense arrays, possessing unique magnetic properties, are eagerly anticipated for inexpensive and scalable fabrication technologies. This study reports a facile method to fabricate arrays of magnetic wires directly assembled from well-dispersed α″-Fe16N2/Al2O3 and Fe3O4 nanoparticles with average diameters of 45 nm and 65 nm, respectively. The magnetic arrays with a height scale of the order of 10 mm were formed on substrate surfaces, which were perpendicular to an applied magnetic field of 15 T. The applied magnetic field aligned the easy axis of the magnetic nanoparticles (MNPs) and resulted in a significant enhancement of the magnetic performance. Hysteresis curves reveal that values of magnetic coercivity and remanent magnetization in the preferred magnetization direction are both higher than that of the nanoparticles, while these values in the perpendicular direction are both lower. Enhancement in the magnetic property for arrays made from spindle-shape α″-Fe16N2/Al2O3 nanoparticles is higher than that made from cube-like α″-Fe16N2/Al2O3 ones, owing to the shape anisotropy of MNPs. Furthermore, the assembled highly magnetic α″-Fe16N2/Al2O3 arrays produced a detectable magnetic field with an intensity of approximately 0.2 T. Although high-intensity external field benefits for the fabrication of magnetic arrays, the newly developed technique provides an environmentally friendly and feasible approach to fabricate magnetic wires in highly dense arrays in open environment condition.

Precisely tailored synthesis of hexagonal hollow silica plate particles and their polymer nanocomposite films with low refractive index.

Hollow silica particles are desirable for numerous applications, however, designing hollow silica materials with varying hollow structures and shapes remains a significant challenge. Herein, a strategy for the precisely controlled synthesis of hexagonal-shaped hollow silica plate (HHSP) particles was successfully prepared via a sol-gel method at room temperature, using tetraethyl orthosilicate (TEOS) as a silica precursor and zinc oxide (ZnO) particles as a colloidal template. The effect of reaction time was carried out to control the structure and morphology of HHSP particles, and the thickness of silica shell can be tuned in the range from 12.2 to 43.2 nm by adjusting the TEOS/ZnO molar ratios. In addition, the polymer/HHSP composite thin films were prepared using poly(methyl methacrylate) (PMMA) matrix and surface modified HHSP particles by grafting silane coupling agents. High transmittance values were observed (>95%) for the composite thin films (5 µm in thickness, 0.1-1.0 wt% HHSP) in the ultraviolet and visible regions. Furthermore, the refractive index of HHSP particles was observed to be 1.28, which is significantly lower than dense silica (n = 1.46). These results suggest that the approach adopted herein will open up opportunities for the development of a new generation of film materials with a low refractive index.