Nanoarchitectonics Solution Plasma Polymerization of Amino-Rich Carbon Nanosorbents for Use in Enhanced Fluoride Removal.

Amino-functionalized carbon (NH2C) is an effective adsorbent in removing pollutants from contaminated water because of its high specific surface area and electrical charge. In the conventional preparation method, the introduction of amino groups onto the carbon surface is limited, resulting in low pollutant adsorption. Herein, we present simultaneous carbonization and amination to form NH2C via electrical discharge of nonequilibrium plasma, and the resultant material is applied as an effective adsorbent in fluoride removal. The simultaneous process introduces numerous amino groups into the carbon framework, enhancing the adsorption efficiency. The fluoride adsorption capacity is approximately 121.12 mg g-1, which is several times higher than those reported in previous studies. Furthermore, computational modeling is performed to yield deeper mechanistic insights into the molecular-level adsorption behavior. These data are useful in designing and synthesizing advanced materials for applications in water remediation.

Layer-Stacking Sequence Governs Ion-Storage in Layered Double Hydroxides.

In layered materials, the layer-stacking sequence allows the tuning of ion transport and storage properties by modulating the host-ion interactions. However, unlike in the case of cations, the relationship between the stacking sequence and anion transport and storage properties is less clearly understood. Herein, we demonstrate that the stacking sequence governs the nitrate-storage properties of layered double hydroxides (LDHs); the 2H1 polytype enhances the nitrate-storage capacity to 400% of that of the 3R1 polytype. A quartz crystal microbalance with dissipation monitoring combined with multimodal ex situ experiments indicated that the high ion-storage capacity of the 2H1 polytype originates from the soft nature of LDHs lattices, which facilitates nitrate with minimal lattice changes. In contrast, the rigid lattice of the 3R1 sequence requires a notably large lattice expansion, which is detrimental to ion storage. Our findings can aid the rational design of anion-host interaction-derived functionalities.

High Li-Ion Selectivity of Five-Coordinate Layered Titanate K2Ti2O5.

Selectivity of ion exchangers is an important topic in adsorption science owing to its specific application in resource recovery and environmental remediation. In this study, the cation exchange property of the submillimeter-sized five-coordinate K2Ti2O5 (KTO) crystals is demonstrated. Adsorption isotherm measurements were performed on KTO crystals ion-exchanged with alkali metal cations including Li+, Na+, Rb+, and Cs+. The maximum adsorption amounts of Li+, Na+, Rb+, and Cs+ on KTO were 2.70, 1.15, 0.59, and 0.42 mmol g-1, respectively, which is contradictory to the "normal" selectivity sequence (Cs+ > Rb+ > K+ > Na+ > Li+) of conventional ion exchangers, including clays and organic resins. The Kielland plots for the Li+ and Cs+ exchange experiments showed preferential Li+ adsorption on KTO, which supports the high Li+ selectivity. The interlayer distance for M+-exchanged KTO (M = Li, Na, Rb, and Cs) was dependent on cation type. Raman and X-ray absorption near-edge structure spectroscopic analyses of the KTO samples indicated that certain Ti species in KTO underwent hydrolysis, and thereby formed hydroxyl groups on the KTO surface during ion exchange. The origin of the high Li+ selectivity of KTO is discussed herein based on experimental characterization results.

Critical role of water structure around interlayer ions for ion storage in layered double hydroxides.

Water-containing layered materials have found various applications such as water purification and energy storage. The highly structured water molecules around ions under the confinement between the layers determine the ion storage ability. Yet, the relationship between the configuration of interlayer ions and water structure in high ion storage layered materials is elusive. Herein, using layered double hydroxides, we demonstrate that the water structure is sensitive to the filling density of ions in the interlayer space and governs the ion storage. For ion storage of dilute nitrate ions, a 24% decrease in the filling density increases the nitrate storage capacity by 300%. Quartz crystal microbalance with dissipation monitoring studies, combined with multimodal ex situ experiments and theoretical calculations, reveal that the decreasing filling density effectively facilitates the 2D hydrogen-bond networking structure in water around interlayer nitrate ions along with minimal change in the layered structure, leading to the high storage capacity.

Single-Step Topochemical Synthesis of NiFe Layered Double Hydroxides for Superior Anion Removal from Aquatic Systems.

Layered double hydroxides (LDHs) have attracted significant attention as adsorbents for the removal of anions from wastewater. However, it is challenging to develop a simple, economical, and environmentally friendly method for fabricating efficient LDH adsorbents. In this paper, we present an alternative approach for preparing a superb NiFe LDH adsorbent via a single-step topochemical synthesis method based on density functional theory (DFT) calculation. The NiFe LDH adsorbent [Ni0.75Fe0.25(OH)2]·(CO3)0.125·0.25H2O was obtained via the topotactic transformation of an oxide precursor (NaNi0.75Fe0.25O2), which was prepared by utilizing the high-temperature flux method, in ultrapure water. When the oxide precursor was soaked in ultrapure water, the host layer valence state changed from Ni3+ and Fe3+ to Ni2+ and Fe3+, and carbonate (CO32-) ions were simultaneously intercalated in the interlayer. Thereafter, the CO32- ions were deintercalated by Cl- ions to increase the adsorption capacity. The adsorbent exhibited high crystallinity, cation state, and porosity, and unique particle shape. In addition, it showed superior adsorption capacities of approximately 194.92, 176.15, and 146.28 mg g-1 toward phosphate, fluoride, and nitrate ions, respectively. The adsorption capacity toward all the anions reached over 70% within 10 min. The adsorption behavior was investigated by performing from adsorption kinetics, isotherm, and thermodynamics studies. The results showed that the anions were endothermically and spontaneously chemisorbed through an ion exchange process onto the adsorbent in a monolayer. In addition, the as-prepared NiFe LDH adsorbent showed high stability after multicycle testing.

Flux Growth of Single-Crystalline Hollandite-Type Potassium Ferrotitanate Microrods From KCl Flux.

Hollandite-type crystals have unique and interesting physical and chemical properties. Here, we report the flux growth of hollandite-type single-crystalline potassium ferrotitanate (KFTO) with faceted surface features from a KCl flux. We varied the flux growth conditions, including the kind of flux, holding temperature, and solute concentration for growing faceted crystallites. KCl was found to be the best flux to grow the single-crystalline KFTO particles, while heating at or above 900°C was needed to yield the KFTO single crystals. The crystal growth was only weakly dependent on the solute concentration. Next, we characterized the grown single crystals and discussed the manner of their growth from the KCl flux. TEM images with clear electron diffraction spots indicated that the KFTO crystals grew along the <001> direction to form microrods ~10 µm in size. DFT calculation results indicated that the surface energy of the (100) face is lower than that of the (001) face. Based on these characterization results, we proposed a possible growth mechanism of the KFTO crystals.

Favorable Intercalation of Nitrate Ions with Fluorine-Substituted Layered Double Hydroxides.

Understanding and controlling confined nanospace to accommodate substrates and promote high ion conduction are essential to various fields. Layered double hydroxides (LDHs) have emerged as promising candidates for anion exchangers using the interlayer nanospace in their crystal structures. Miyata reported in 1983 that the affinity of anions for intercalation with most major Mg-Al LDHs increased in the following order: NO3- < Br- < F- < SO42- < HPO32-. Attempts to alter the affinity with different metal cations (M2+ and M3+) have been unsuccessful. Analyses of the crystalline structures of LDHs, positively charged host layers, interlayer anions, and interlayer water molecules indicate that they inevitably interact through hydrogen bonding. In other words, the affinity of LDHs for anions is controlled by tuning the hydrogen bonding. In this study, we prepared fluorine-substituted LDHs (F-LDHs) with different Mg/Al ratios by partially replacing the OH structural groups, which originated from the host layer, with fluorine atoms; the resulting change in affinity was investigated. The distribution coefficient, which is a useful indicator of the affinity of an LDH for a particular anion, was examined. The results showed that only F-LDHs with Mg/Al ratios of 3.5 exhibited high affinity, especially for NO3- ions, and the affinity increased in the following order: HPO42- < SO42- < F- < Br- < NO3-. The separation factors of these specific F-LDHs with respect to both NO3-/F- and NO3-/SO42- were higher than that of LDHs with other compositions by 1 order of magnitude. Raman spectroscopy above 3000 cm-1 revealed that the fluorine substitution of LDHs significantly changed the hydrogen bonding nature in the interlayer space. Highly electronegative fluorine atoms significantly decrease the extent of hydrogen bonding interactions between OH structural groups and both interlayer water molecules and anions, wherein steric effects are induced by the shrunken interlayer space, and van der Waals forces are revealed to be the predominant interaction with anions. Therefore, the highest affinity was observed for NO3- ions in F-LDHs.

Highly Crystalline Ni-Co Layered Double Hydroxide Fabricated via Topochemical Transformation with a High Adsorption Capacity for Nitrate Ions.

Layered double hydroxide (LDH) has emerged as promising candidates for removing harmful oxoanions (i.e., SO42-, HPO42-, and NO3- ions) from wastewater because of their intrinsic ability to accommodate anionic species in the interlayer space. Highly crystalline [Ni0.67Co0.33(OH)2]Cl0.29·0.53H2O (Ni-Co LDH) particles with an exceptionally high anion-exchange capacity of 58.8 mg g-1 and a distribution coefficient (Kd) of 2396 mL g-1 for NO3- ions were successfully prepared by the flux method and a topochemical strategy. Layered Na0.97Ni0.67Co0.33O2 (NNCO) was prepared using a high-temperature flux and used as a starting material for topotactic transformation consisting of oxidative hydrolysis with KOH and NaClO and subsequent reduction with H2O2 and NaCl. During the transformation from NNCO to Ni-Co LDH, a drastic change in the valences of the Ni and Co belonging to the host layer and in the cationic and anionic species occurs in interlayer space; the valences of the Ni and Co in NNCO were increased from Ni2+,3+ and Co2+,3+ to Ni3+ and Co2+,3+,4+ by an oxidative hydrolysis reaction with simultaneous intercalation of K+ ions and deintercalation of Na+ ions, and subsequently decreased from Ni3+ and Co2+,3+,4+ to Ni2+ and Co2+,3+ by a reduction reaction with simultaneous intercalation of anionic species such as CO32- and Cl- ions and deintercalation of Na+ and K+ ions. Through synchrotron powder X-ray diffraction analysis and Rietveld refinement, the resultant Ni-Co LDH was clearly shown to exhibit high crystallinity with less compositional deviation even after topochemical transformation in comparison with the one prepared by traditional coprecipitation and solid-state methods. Furthermore, the adsorption isotherm for NO3- ions elucidated that homogeneous adsorption sites are consistently constructed in the crystal structure, which could be found from the fitting to a Langmuir curve, with the R2 value being 0.98. This work opens up a new route for the fabrication of excellent not only ion-exchangeable but also ion-conductive inorganic materials for direct utilization in environmental and energy-storage processes.

Accelerated nanoparticles synthesis in alcohol-water-mixture-based solution plasma.

An extraordinary high-speed synthesis of gold nanoparticles (AuNPs) was discovered by synthesizing the AuNPs in ethanol-water mixtures using a solution plasma process (SPP). The influence of the ethanol mole fraction (χethanol) in the ethanol-water mixtures on the reduction rate of gold chloride ions to AuNPs under the SPP system was studied. The results indicated that the reaction rate of the AuNPs synthesis exhibited a maximum value (i.e. 35.2 times faster than in a pure water system) at the significant point where the partial molar volumes of ethanol and water changed drastically.

Verification of Radicals Formation in Ethanol-Water Mixture Based Solution Plasma and Their Relation to the Rate of Reaction.

Our previous research demonstrated that using ethanol-water mixture as a liquid medium for the synthesis of gold nanoparticles by the solution plasma process (SPP) could lead to an increment of the reaction rate of ∼35.2 times faster than that in pure water. This drastic change was observed when a small amount of ethanol, that is, at an ethanol mole fraction (χethanol) of 0.089, was added in the system. After this composition, the reaction rate decreased continuously. To better understand what happens in the ethanol-water mixture-based SPP, in this study, effect of the ethanol content on the radical formation in the system was verified. We focused on detecting the magnetic resonance of electronic spins using electron spin resonance spectroscopy to determine the type and quantity of the generated radicals at each χethanol. Results indicated that ethanol radicals were generated in the ethanol-water mixtures and exhibited maximum quantity at the xethanol of 0.089. Relationship between the ethanol radical yield and the rate of reaction, along with possible mechanism responsible for the observed phenomenon, is discussed in this paper.