Ion-exchange Reaction Research Articles

3D model of a stable triangle LiF–NaBr–KBr four-component reciprocal system Li+, Na+, K+ || F-, Вr-

A 3D model of the phase equilibrium states of the quasi-three-component system LiF–NaBr–KBr, which is a stable triangle of the four-component reciprocal system Li+, Na+, K+ || F-, Br-, has been constructed. Based on the 3D-model, polythermal, isothermal sections and the polytherm of phase crystallization were constructed for the first time. Two polythermal sections contain wide areas of boundary solid solutions based on sodium and potassium bromide. In an isothermal section at 650 оC, the fields of the liquid phase and the coexisting two and three phases are delimited. The crystallization polytherm is represented by three fields. In the crystallization field of lithium fluoride, the area of separation of two liquids is limited. The direction of the ion exchange reaction 2LiBr + NaF + KF = 2LiF + NaBr + KBr was confirmed by thermodynamic calculations at temperatures of 400, 600, 800, 1000K. The exothermic nature of the exchange reaction is confirmed by taking a DTA heating curve for a mixture of powders from 50% LiBr + 25% NaF + 25% KF, and the phase composition of the reaction products LiF + NaBr(OTR) + KBr(OTR) is confirmed by X-ray phase analysis data, where OTR is limited solid solution.

Selective Sorption of Noble Metals on Polymer Gel Modified with Ionic Liquid.

The solid phase extraction of Au, Ir, Pd, Pt, and Rh on a polymer gel modified with ionic liquid containing methylimidazolium groups (MIA-PG) has been investigated. The positively charged surface of the sorbent is highly suitable for the sorption of stable chlorido complexes of the studied analytes, while the retention of base metals Cu, Fe, Ni, Zn, and Mn is negligible. Optimization experiments performed showed that, at 0.05 M HCl, the degree of sorption of Au, Ir, Pd, and Pt is above 95%, and only for Rh, the maximum degree is 65%; complete elution is achieved in the mixture of thiourea in HCl. The results obtained from the equilibrium adsorption studies are fitted in various adsorption models, such as Langmuir and Freundlich, and the model parameters have been evaluated. The kinetics analysis indicated that the adsorption of Au, Ir, Pd, Pt, and Rh onto the sorbent follows the pseudo-second-order model. Intraparticle diffusion and ion exchange reactions were the rate-limiting steps. Analytical procedures were developed for Pd, Pt, and Rh determination in road dust and soil and for Au determination in copper ore and copper concentrate. The procedures are validated by the analysis of certified reference materials. Analytical figures of merit confirmed their applicability in routine laboratory practice.

Research on the synthesis process and properties of dinitramide compounds for applications in propellants and explosives

Dinitramide compounds are characterized by a high oxygen and nitrogen content and the absence of halogens in their molecular structure, making them suitable for environmentally friendly new-generation propellants and explosives. This study outlines the optimization of the synthetic pathways for these compounds, including the preparation of guanylurea dinitramide (GUDN) via nitration and the synthesis of potassium dinitramide (KDN), ammonium dinitramide (ADN), and guanidinium dinitramide (GDN) through ion-exchange reactions. Additionally, the resulting dinitramide compounds were systematically evaluated for their physicochemical properties, ballistic characteristics, and spectral features. The findings demonstrate that these compounds exhibit high synthesis efficiency and possess properties conducive to their effective application in propellant and explosive formulations.

Preparation, Characterization, and Adsorption Performance of H2TiO3 Lithium Ion Sieves with Homogeneous Nanoparticles: Kinetics, Thermodynamics, and Mechanism Analysis

AbstractLi2TiO3 precursor with layered structure is successfully prepared by template‐free method using anatase TiO2 and Li2CO3, followed by the treatment of dilute hydrochloric acid, which leads to obtaining H2TiO3 lithium ion sieve nanoparticles with uniform dispersion and small size. The adsorption performance and mechanism of the H2TiO3 are being studied. The experimental results show that the H2TiO3 lithium ion sieve has a large BET specific surface area (19.10 m2 g−1) and good thermal stability. At the same time, it also has a high adsorption rate and adsorption capacity (55.13 mg g−1) towards Li+ in solution due to its high dispersibility and uniformity of particle size, which can expose more adsorption sites in LiCl solution. The adsorption capacity of the H2TiO3 lithium ion sieve can reach 46.63 mg g−1, which achieves 84.58% of the equilibrium adsorption capacity. The equilibrium adsorption parameters follow the Langmuir model perfectly, demonstrating that Li+ undergoes monolayer adsorption. The results of thermodynamic and kinetic analysis show that the adsorption behavior of H2TiO3 is spontaneous and conforms to the pseudo‐second‐order kinetic model, indicating the adsorption process is controlled by chemosorption. In addition, after five adsorption/desorption cycles, the H2TiO3 lithium ion sieve still shows a high adsorption capacity of 46.15 mg g−1, and the dissolution loss of titanium is only 0.14%, which shows that the cycle stability is excellent. XPS and zeta potential analyses illustrate that the adsorption mechanism of Li+ on the H2TiO3 is an ion exchange reaction between Li+ and H+, combined with the electrostatic attraction of the adsorbent surface. Additionally, the adsorption performance of H2TiO3 lithium ion sieve in West Taijinaier Salt Lake brine was tested, and the adsorbent material proves itself is a perspective candidate for lithium extraction from aqueous lithium resources.

Remediation of heavy metal contaminated soil in mining areas with vaterite-type biological calcium carbonate

In recent years, research on the remediation of heavy metal contaminated soil by microbially induced carbonate precipitation (MICP) technology has yielded significant findings. However, when utilizing MICP for remediation in situ, urea and calcium chloride may produce high concentrations of NH4+ and Cl-, which subsequently cause secondary pollution. If the biological calcium carbonate (Bio-CaCO3) produced by MICP is employed as a highly efficacious adsorbent, secondary pollution can be avoided while remediating heavy metal pollution. In this study, vaterite-type Bio-CaCO3 was prepared under the regulation of sophorolipids, and the remediation effect and mechanisms for heavy metal contaminated soil were investigated. The results demonstrated that sophorolipids facilitate the formation and stabilization of vaterite-type Bio-CaCO3. The addition of vaterite-type Bio-CaCO3 could notably increase the content of soil organic matter, enhance soil urease activity, and reduce soil catalase activity. On the 30th day of remediation with vaterite-type Bio-CaCO3, the active state content of Pb and Cd in the soil exhibited a decrease of 41.23% and 35.00%, respectively. Additionally, the exchangeable state content demonstrated a reduction of 6.61% and 8.48%, while the carbonate-bound state exhibited an increase of 12.05% and 13.89%, respectively. The principal mechanisms for the remediation of heavy metal contaminated soil by vaterite-type Bio-CaCO3 may be attributed to ion exchange, chemical precipitation, physical adsorption, and complexation reactions. The analysis of the microbial community structure demonstrated that vaterite-type Bio-CaCO3 could enhance the abundance of multiple genera with urease-producing genes, including Pseudomonas, Staphylococcus, and Bacillus while maintaining the soil biodiversity. This study provides a new idea for the remediation of heavy metal contaminated soil around the mining area and offers technical support for the construction of green mines.

NaZr2(PO4)3 - a cubic langbeinite-type sodium-ion solid conductor.

The synthesis of langbeinite-type phosphates with small cations such as Li+ or Na+via a high-temperature solid-state reaction is a challenging task due to the predominant formation of a related NaSICON-type phase. This work reports on the synthesis route, crystal structure, thermal behavior, and Na-conductive properties of the langbeinite-type NaZr2(PO4)3 prepared by a mechanochemically activated ion-exchange reaction between hydrothermally prepared NH4Zr2(PO4)3 and NaNO3. The crystal structure of NaZr2(PO4)3 is refined based on X-ray diffraction data and validated by Fourier-transformed infrared spectroscopy. NaZr2(PO4)3 is found to be stable up to 730 °C, undergoing a transformation into the NaSICON phase with further heating. Notably, in the 25-500 °C range, the material shows negative thermal expansion. The Na+ conductivity within the range of 50-225 °C amounts to 1.7 × 10-8 S cm-1 at 50 °C and 1 × 10-6 S cm-1 at 225 °C with an activation energy of 0.44 eV, accompanied by a sufficiently low (∼10-12 S cm-1) electronic conductivity. The bandgap of 4.44 eV and the electrochemical stability window covering the 1.39-4.18 V vs. Na/Na+ range are calculated using density functional theory. The obtained results open up opportunities for designing langbeinite-structured phosphates as potential solid electrolytes for Na-ion batteries.

Performance and mechanism of amino-functionalized hydroxyapatite for uranium removal from strong acidity uranium wastewater

The extraction of uranium generates substantial volumes of acidic wastewater loaded with uranium, thereby posing imminent threats to ecological systems and human wellbeing. Consequently, the development of highly effective adsorbent materials for uranium sequestration under strong acidic conditions has become paramount. The amino group contains a lone pair of electrons and is a highly reactive nucleophilic group with a strong affinity for uranium. Herein, we report the amino-functionalized materials (HAP-L-1NH2, HAP-L-2NH2, and HAP-L-3NH2) derived from sodium citrate-modified hydroxyapatite (HAP-L) through a combination of ultrasonic heating and grafting with varying concentrations of 2-amino-1,3-propanediol. The study delved into their performance and underlying mechanisms for uranium removal from acidic wastewater. The findings indicate that an optimal pH of 3.0 favors uranium adsorption for all the materials, with adsorption equilibrium achieved within 30 min. Their respective maximum uranium adsorption capacities stand at 826.44, 990.09, 1060.21, and 884.95 mg g−1, significantly enhancing the adsorptive prowess of amino-functionalized HAP-L materials. The kinetics and thermodynamics manifest that spontaneous endothermic chemisorption occurs on a homogenous monolayer during the adsorption process. Notably, HAP-L-2NH2 robust resilience to interfering ions and exceptional recyclability. After eight cycles of adsorption-desorption, HAP-L-2NH2 retains a uranium adsorption rate of 93.96 % with a stable chemical structure. Application of HAP-L-2NH2 in treating real-world acidic uranium wastewater led to a notable increase in pH from 2.87 to 3.92 and a substantial reduction in uranium concentration from 0.883 mg L−1 to 0.0104 mg L−1. Uranium removal by HAP-L-2NH2 is primarily governed by ion exchange, electrostatic interaction, and co-precipitation reactions.

Experimental study on the stabilization of marine soft clay as subgrade filler using binary blending of calcium carbide residue and fly ash

This study endeavors to realize the concurrent utilization of marine soft clay (MSC) and industrial waste, specifically calcium carbide residue (CCR) and fly ash (FA), through a series of experimental investigations. The optimal ratio between CCR and FA, as well as the efficacy of the composite agent (CF–1), were examined, and an empirical equation associating the unconfined compressive strength (qu) of stabilized MSC was developed through unconfined compressive strength (UCS) tests. Microscopic analyses, including X–ray diffraction (XRD), scanning electron microscopy (SEM), and energy–dispersive spectroscopy (EDS), were employed to unveil the intrinsic mechanisms underlying CF–1 stabilized MSC. Subsequently, the suitability of CF–1 solidified MSC as a roadbed filler was ascertained through laboratory tests. Results revealed the optimum CCR:FA ratio for CF–1 to be 4:1, demonstrating superior curing effects compared to individual components such as Portland cement (PC), CCR, and FA, with commendable environmental and economic benefits. The developed empirical equation exhibited effectiveness in predicting the qu of CF–1 solidified MSC under varying curing dates (T) and dosages (Wg) conditions. Characterization through XRD, SEM, and EDS identified the primary products formed within the stabilized MSC matrix with CF–1 as comprising calcium–silicate–hydrate (C–S–H) gel, calcium–aluminate–hydrate (C–A–H) gel, and a minor amount of calcite. As T and Wg increased, the reduction in pores between soil particles enhanced the structural integrity and macro–strength of the cured MSC. The failure pattern of CF–1–solidified MSC elementary samples depended on the CF–1 dosage and curing duration. The solidification mechanism of CF–1 on MSC involved pozzolanic, ion exchange, and carbonation reactions. CF–1 solidified MSC satisfied all the specified requirements for roadbed filler in the relevant code, demonstrating substantial potential for in–situ solidification projects involving MSC.

Revealing the Chemical and Structural Complexity of Electrochemical Ion Exchange in Layered Oxide Materials.

Soft chemistry techniques, such as ion exchange, hold great potential for the development of battery electrode materials that cannot be stabilized via conventional equilibrium synthesis methods. Nevertheless, the intricate mechanisms governing ion exchange remain elusive. Herein, we investigate the evolution of the long-range and local structure, as well as the ion (de)intercalation mechanism during electrochemical Li-to-Na ion exchange initiated from an O3-type lithium-layered oxide cathode. The in situ-formed mixed-cation electrolyte leads to competitive intercalation of Li and Na ions. While Li ion intercalation predominates at the beginning of initial discharge, Na ion cointercalation into a different layer results in ion redistribution and phase separation, with the emergence of a P3-Na phase alongside an O3-Li phase. Further, this study spatially resolves the heterogeneous nature of electrochemical ion exchange reactions within individual particles and provides insights into the correlations between local Ni redox processes and phase separation. Overall, electrochemical ion exchange leads to a mixed-phase cathode and alters its reaction kinetics. Those findings have important implications for the development of new metastable materials for renewable energy devices and ion separation applications.

Hydrogeochemical and isotopic investigations of groundwater in the reclaimed desert located between EL Nasr canal and Mariut Tableland, NW Coast, Egypt

A complete understanding of groundwater dynamics and its interaction with surface water under the impact of agricultural activities is vital for local agriculture, ecology, and residents of dry regions, which is not commonly recognized in arid areas. This research outlines the geochemical characteristics, recharge sources, and potential factors impacting groundwater quality in a new land reclamation located in the small basin of Abu Mina, which is part of the Western Nile Delta region.1 Thirty-one groundwater samples and two surface water samples were collected in 2021 to represent the Pleistocene aquifer and were subjected to multivariate statistical, hydrochemical, and stable isotope analyses. Data analysis demonstrates that Na+ > Ca2+ > Mg2+ > K+ and SO42– > Cl– > HCO3– > NO3– are the predominant cations and anions, respectively. Groundwater salinity ranged from 465.60 to 6455.18 mg/l, with slightly alkaline. Most of the water samples fall into one of three types of facies: Ca–Cl, Na–Cl, and Mixed Ca–Mg–Cl, in decreasing order. The meteoric genesis index (r2) indicates that deep meteoric water percolation dominates the Pleistocene aquifer. The aquiline diagrams, correlation matrix, and different ionic ratios indicate that evaporation, reverse ion exchange reactions, and the dissolution of carbonate and silicate minerals are the main processes governing groundwater chemistry. Factor analysis (FA) indicated that three factors explain groundwater hydrochemistry, accounting for 71.98% of the total variance. According to the rotating components matrix (F1–F3), the chemistry of the Quaternary aquifer is principally affected by evaporation, ion exchange reactions, and anthropogenic influences. Additionally, salinity increases due to the return flow of irrigation activities and mixing between old and recent water. The stable isotopes (δ18O and δ2H) indicate that the Quaternary aquifer receives groundwater recharge through the return flow of excess irrigation and canal seepage. Under desert reclamation conditions, groundwater salinization processes should be given special consideration. All groundwater samples are appropriate for agricultural irrigation based on the Sodium Adsorption Ratio (SAR), Permeability Index (PI), Percent Sodium (%Na), and Residual Sodium Carbonate (RSC).

Enhancing Flame-Retardant Properties of Polyurethane Composites Using N-β-(Aminoethyl)-γ-aminopropyl Trimethoxysilane and Carbon Black Co-Modified Ammonium Polyphosphate

The search for a straightforward method to obtain efficient, affordable, and long-lasting flame retardants with both desirable flame-retardant and mechanical properties for polyurethane (PU) composites remains a significant challenge. In this study, the surface of ammonium polyphosphate (APP) was modified using N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane (KH792) via an ion-exchange reaction, and the modified APP was coated with nanoscale carbon black (CB) to obtain CBAPP. CBAPP demonstrated good compatibility within the PU matrix and notably increased the tensile strength of the PU composites. Furthermore, CBAPP significantly enhanced the flame-retardant properties of the PU composites. The CBAPP/PU composite with a CBAPP mass fraction of 20% achieved a limiting oxygen index of 41.5% and a UL-94 class of V-0. According to the results of this study, our modification approach can be applied to develop other high-performance flame-retardant polymer-based composites, representing a significant contribution to the field of fire safety materials.

Investigating the Potential of Microbially Induced Carbonate Precipitation Combined with Modified Biochar for Remediation of Lead-Contaminated Loess

Lead (Pb) contamination in loess poses a significant environmental challenge that impedes sustainable development. Microbially induced carbonate precipitation (MICP) is an innovative biomimetic mineralization technology that shows considerable promise in remediating soil contaminated with heavy metals. However, the toxicity of lead ions to Bacillus pasteurii reduces the efficiency of mineralization, subsequently diminishing the effectiveness of remediation. Although biochar can immobilize heavy metal ions, its adsorption instability presents a potential risk. In this study, we first compared the pH, electrical conductivity (EC), unconfined compressive strength (UCS), permeability coefficient, and toxicity leaching performance of lead-contaminated loess specimens remediated using biochar (BC), red mud (RM), red-mud-modified biochar (MBC), and MICP technology. Additionally, we evaluated the mechanism of MICP combined with varying amounts of MBC in remediating lead-contaminated loess combing Zeta potential, X-ray diffraction (XRD) analyses, and scanning electron microscopy (SEM) tests. The results showed that MICP technology outperforms traditional methods such as RM, BC, and MBC in the remediation of lead-contaminated loess. When MICP is combined with MBC, an increase in MBC content results in a higher pH (8.71) and a lower EC (232 us/cm). Toxic leaching tests reveal that increasing MBC content reduces the lead leaching concentration in loess, with optimal remediation being achieved at 5% MBC. Microscopic analysis indicates that the remediation mechanisms of MICP combined with MBC involve complexation, electrostatic adsorption, ion exchange, and precipitation reactions. The synergistic application of MICP and MBC effectively adsorbs and immobilizes lead ions in loess, enhancing its properties and demonstrating potential for pollution remediation and engineering applications.

Unlocking the potential: Transforming hazardous waste into solid cementitious materials

Incineration fly ash and mineral slag represent hazardous and industrial solid wastes necessitating immediate remediation in China. The liberation and stabilization of heavy metals have erected formidable barriers to their reclamation and repurposing. This study presents a pivotal technology for creating all-solid waste cementitious materials, with the optimal parameters consisting of a dosage of 55.773% incineration fly ash, 38.822% cementitious materials dosage, and 5.405% adhesive powders dosage. Furthermore, a comprehensive evaluation model has been developed to assess the performance of these materials. Several extraction procedure experiments were conducted to investigate the leaching behavior of heavy metals under various leaching scenarios, which suggests the diffusion coefficients of heavy metals under the optimal ratio are all less than 3 × 10–13 m2/s, affirming the effective stabilization and the absence of potential migration risks. The primary mechanisms of solidification involved include ion exchange reactions for charge balance and the encapsulation of precipitates through cementation, both of which contribute to the solidification of heavy metals. The findings will illuminate advanced strategies for reducing waste, enhancing resource efficiency, and promoting environmentally friendly building practices, as well as provide a promising avenue for achieving sustainability goals in construction projects, leading to reduced environmental impact and improved long-term sustainability. The integration of ACM-SW can pave the way for transformative advancements in sustainable building practices, ultimately leading to a more environmentally friendly and resilient built environment.

Modulation between capacitor and conductor for a redox-active 2D bis(terpyridine)cobalt(II) nanosheet via anion-exchange

Ionic polymers are intriguing materials whose functionality arises from the synergy between ionic polymer backbones and counterions. A key method for enhancing their functionality is the post-synthetic ion-exchange reaction, which is instrumental in improving the chemical and physical properties of polymer backbones and introducing of the functionalities of the counterions. Electronic interaction between host polymer backbone and guest ions plays pivotal roles in property modulation. The current study highlights the modulation of responses to external electric field in cationic bis(terpyridine)cobalt(II) polymer nanofilms through anion-exchange reactions. Initially, as-prepared chloride-containing polymers exhibited supercapacitor behaviour. Introducing anionic metalladithiolenes into the polymers altered the behaviour to either conductive or insulative, depending on the valence of the metalladithiolenes. This modulation was accomplished by fine tuning of charge-transfer interactions between the bis(terpyridine)cobalt(II) complex moieties and redox-active anions. Our findings open up new avenue for ionic polymers, showcasing their potential as versatile platform in materials science.

Calcium Ion-Coupled Polyphosphates with Different Degrees of Polymerization for Bleeding Control.

The development of efficient hemostatic materials is crucial for achieving rapid hemorrhage control and effective wound healing. Inorganic polyphosphate (polyP) is recognized as an effective modulator of the blood coagulation process. However, the specific effect of polyP chain length on coagulation is not yet fully understood. Furthermore, calcium ions (Ca2+) are essential for the coagulation process, promoting multiple enzyme-catalyzed reactions within the coagulation cascade. Hence, calcium ion-coupled polyphosphate powders with three different degrees of polymerization (CaPP-n, n = 20, 50, and 1500) are synthesized by an ion-exchange reaction. CaPP exhibits a crystalline phase at a low polymerization degree and transitions to an amorphous phase as the polymerization degree increases. Notably, the addition of Ca2+ enhances the wettability of polyP, and CaPP promotes hemostasis, with varying degrees of effectiveness related to chain length. CaPP-50 exhibits the most promising hemostatic performance, with the lowest blood clotting index (BCI, 12.1 ± 0.7%) and the shortest clotting time (302.0 ± 10.5 s). By combining Ca2+ with polyP of medium-chain length, CaPP-50 demonstrates an enhanced ability to accelerate the adhesion and activation of blood cells, initiate the intrinsic coagulation cascade, and form a stable blood clot, outperforming both CaPP-20 and CaPP-1500. The hemostatic efficacy of CaPP-50 is further validated using rat liver bleeding and femoral artery puncture models. CaPP-50 is proven to possess hemostatic properties comparable to those of commercial calcium-based zeolite hemostatic powder and superior to kaolin. In addition, CaPP-50 exhibits excellent biocompatibility and long-term storage stability. These results suggest that CaPP-50 has significant clinical and commercial potential as an active inorganic hemostatic agent for rapid control of bleeding.

Gold recovery from chloride leach solution of TCCA using D301 anion exchange resin and elution with thiourea

Trichloroisocyanuric acid (TCCA), which is used for gold leaching, is an alternative to cyanidation due to its lower toxicity and higher efficiency. This study investigated the gold recovery procedures from highly effective chloride leaching solution using the D301 resin. This approach prevented the inhibition of gold adsorption when using activated carbon. Herein, the optimal conditions for gold adsorption were discussed, including establishing adsorption kinetics and isotherms, and calculating adsorption activation energy. Additionally, SEM (Scanning Electron Microscope), FTIR (Fourier Transform Infrared Spectroscopy), and XPS (X-ray Photoelectron Spectroscopy) techniques were used to reveal the mechanism of gold adsorption using D301 resin. Under optimal conditions (pH 4.0, temperature 25 °C, time 120 min), an average adsorption percentage of 99.2% was achieved. Analysis of the adsorption data confirmed that gold adsorption followed the pseudo-second-order kinetic model and Freundlich adsorption isotherm. The calculated activation energy was 9.69 kJ mol−1, indicating a predominance of physical adsorption involving ion exchange reactions with protonated tertiary amine groups in the D301 resin beads. Furthermore, among various eluents tested in desorption experiments, a solution containing a mixture of thiourea and hydrochloric acid with 0.4 mol L−1 and 0.8 mol L−1, respectively, demonstrated superior efficiency, achieving a successful desorption percentage reaching 95.7 ± 0.3% within 80 min. After three cycles of resin regeneration, the regeneration efficiency reached 91.2% while maintaining an average adsorption percentage of 95.3%.

Lanthanide (Sm, Dy) Complexes with the 9,10-Phenanthrenediimine Redox-Active Ligand: Synthesis and Structures

The complex formation of the redox-active ligand bis(N, N’-2,6-diisopropylphenyl)-9,10-phenanthrenediimine (DippPDI) with alkaline metal (Li, K) and lanthanide (Sm, Dy) cations is studied. The reduction of DippPDI with an alkaline metal excess affords the dianionic form of the ligand (DippPDA2–), which crystallizes with the potassium cation as the coordination polymer [K2(DippPDA)(Thf)3] (Thf is tetrahydrofuran, THF). The reaction of equimolar amounts of the lithium salt with the dianionic form of the ligand and neutral diimine affords the lithium complex with the radical-anion form (DippPSI•–) crystallized as [Li(DippPSI)(Thf)2]. The samarium(III) complex [SmCp*(DippPDA)(Тhf)] (I) is formed by the reduction ofDippPDI with samarocene [Sm (Thf)2] (Cp* is pentamethylcyclopentadienide): both the samarium(II) cation and Cp*– anion are oxidized in the reaction.DippPDI does not react with similar ytterbocene. The dysprosium(III) complexes are synthesized by the ion exchange reactions between DyI3(Thf)3.5 and potassium or lithium salt with theDippPDA2-dianion. Similar complexes [Dy(DippPDA)I(Thf)2] (IIThf) and [Dy(DippPDA)I(Thf)(Et2O)] () are formed in the reactions with the potassium salt depending on the solvent used: a THF-hexane or a diethyl ether-n-hexane mixture, respectively. The coordination of the dysprosium cation by the π system of the conjugated fragment of the NCCN ligand is observed in IIThf, whereas in this coordination is absent. The reaction with Li2(DippPDA) affords the binary complex salt [Li(Тhf)3(Et2O)][DyI2(DippPDA)(Тhf)] (III, crystallization from a THF-Et2O mixture). The crystallization from THF gives the [Li(Тhf)4][DyI2(DippPDA)(Thf)] salt (III') containing the same anion as III. The structures of all new complexes are studied by X-ray diffraction (XRD, CIF files CCDC nos. 2260307–2260313).

The CuS-coated CuO nanostructures grown by ion exchange reaction for efficient photoelectrochemical water splitting

CuO is a promising solar photocathode for hydrogen production. However, it suffers serious photocorrosion in the electrolyte, which hinders the efficiency of photoelectrochemical (PEC) water splitting. In the study, Cu(OH)2 nanowires were in situ grown on copper foils through a straightforward wet chemical oxidation process, followed by annealing in air to synthesize CuO photocathode. To enhance their performance, the surface of CuO photocathode was modified by loading CuS with the ion exchange reaction (IER). Under AM 1.5 G, the CuO photocathode modified by CuS showed a significant improvement in the photo-current density, achieving the highest photo-current density was −4.83 mA·cm−2 at 0 V vs. RHE, which was far superior to the photo-current density (-2.02 mA·cm−2) of pristine CuO photocathode at the same potential. Furthermore, the maximum applied bias photon-to-current efficiency (ABPE) of the CuO/CuS photocathode is 0.77 %, which is superior to that of pristine CuO (0.24 %). The enhanced PEC performance of CuO/CuS photocathode is attributed to the improved light absorption and the efficient separation of photogenerated electron-hole pairs.

Disintegration characteristics and mechanism of red clay improved by steel slag powder

Red clay is prone to softening and disintegration when exposed to water, often triggering severe geological disasters. To enhance its resistance to disintegration, this paper employs a homemade wet-dry cycling disintegration apparatus, combined with XRD, SEM, MIP, and fractal theory, to analyze the effects of different activators on the disintegration characteristics and microscopic mechanisms of SSP-improved soil. Under wet-dry cycling, the disintegration process of SSP-improved soil can be divided into five stages: rapid water absorption, saturation wetting, rapid disintegration, softening and dissolution, and stable non-disintegration. As the activator and SSP content increase, the resistance to disintegration of SSP-improved soil gradually enhances. After the addition of activators, the porosity, pore area, pore length and width, and probability entropy of SSP-improved soil decrease (i.e., 7 % NS < 7 % CSW < 7 % NH < undisturbed soil), while the average shape factor, regional probability distribution index, and fractal dimension increase. This is because activators promote ion exchange, cementation, crystallization, and carbonation reactions in SSP-improved soil, generating a substantial amount of hydration products such as C-S(A)-H, Ca(OH)2 and CaCO3, which fill and encapsulate inter-particle pores, thereby reducing water flow channels within the pores. In contrast, the pore structure between particles in undisturbed soil is simple and well-connected, providing favorable conditions for the migration and dissolution of fine particles and the loss of cementing materials, which accelerates the destruction and disintegration of the soil structure.

(Invited) Synthesis and Visible-Plasmonic Properties of Intermetallic Nanoparticles

The past research on inorganic nanomaterials that exhibit intrinsic localized surface plasmon resonance (LSPR) in the visible region has focused on well-disperse nanoparticles (NPs) including group 11 elements (Au, Ag, and Cu) [1]. Recent theoretical studies on photo-excited electron dynamics in Au NPs have revealed that not only the interband transition but also the screening caused by the vibrations of bound electrons by visible light are important for visible LSPR [2]. However, the correlation between the electronic and crystal structure (as a means of controlling the screening effect) remains unclear because most alloys based on group 11 elements have a face-centered cubic (fcc)-based structure. Here, we show that well-disperse spherical intermetallic Pd-based alloy NPs and Pt-based alloy NPs with non-close packed structure intrinsically exhibit LSPR absorption in the visible region.It is well known that chemical conversion of inorganic NPs via element substitution reactions, such as ion exchange reactions [3] and galvanic replacement reactions, can overcome the difficulties associated with controlling the size, shape, chemical composition, and crystal structure in conventional syntheses [4-6]. Especially, alloying enables us to drastically modulate the electronic properties of metallic NPs. The retained shape of the parent-NPs in element replacement reactions provides an opportunity to obtain non-equilibrium unique structures and even new structures of inorganic NPs. We demonstrate that various Pd-based alloy NPs with a B2 structure were synthesized by the element replacement reactions with Pd–P NPs and showed LSPR in the visible region [7]. On the other hand, we successfully synthesized pseudospherical PtIn2 intermetallic NPs with a C1 structure as uncommon types of visible plasmonic NPs [8].Consequently, we can extract the design principles of intermetallic NPs that exhibit LSPR in the visible region in terms of the crystal and electronic structures as follows. (i) The electronic structure of intermetallic NPs should be similar to that of group 11 element NPs, that is, the sp-band crossing the Fermi level and d-band edge of noble metal like Pt around the visible region. The deeper d-band edge of another base metal like indium less affects the red-shift of LSPR wavelength. (ii) The intermetallic NPs should have non-close packed structure to cause strong screening effect by a small number of d-electrons of noble metal. The intermetallic NPs, which satisfy the above two requirements, are expected to show LSPR in the visible region and serve as novel plasmonic photocatalysts [9].[1] Kawawaki, T.; Teranishi, T. et al., J. Am. Chem. Soc. 2019, 141, 8402–8406.[2] Iida, K.; Noda, M.; Ishihara, K.; Nobusada, K. J. Phys. Chem. A 2014, 118, 11317–11322.[3] Saruyama, M.; Sato, R.; Teranishi, T. Acc. Chem. Res. 2021, 54, 765–775.[4] Wu, H.-L.; Sato, R.; Teranishi, T. et al., Science 2016, 351, 1306–1310.[5] Li, Z.; Saruyama, M.; Asaka, T.; Tatetsu, Y.; Teranishi, T. Science 2021, 373, 332–337.[6] Matsumoto, K.; Sato, R.; Tatetsu, Y.; Teranishi, T. et al., Nat. Commun. 2022, 13, 1047.[7] Sato, R.; Takekuma, H.; Teranishi T. et al., to be submitted.[8] Takekuma, H.; Sato, R.; Iida, K.; Teranishi, T. et al., Adv. Sci., in revision.[9] Lian, Z; Teranishi, T. et al., J. Am. Chem. Soc. 2019, 141, 2446–2450.