Trivalent Metal Research Articles

Tuning the Structure of Layered Hydroxides for Boosting Energy Application Performance

We are currently on a race against the clock to protect our planet from greenhouse gas emissions. The solution could be inspired from mother nature talking about renewable energies or so-called green energies including wind, solar, hydraulic, biomass and so on, which allows us to reduce the fossil fuels consumption. However, these kinds of energy devices should be coupled to an energy storage system such as batteries and supercapacitors to compensate the absence of wind and sun. For this purpose, we are looking forward to developing strong energy and power application systems by focusing on the development of novel electrode materials.Among 2D materials, layered hydroxides emerge as one of the most attractive electrode materials based on earth-abundant metals, at the same time inside of this family, three type can distinguish: the first one is the Brucite-like structure1 (β-structure) where the metal is arranged in the octahedral position and the interlayer space is defined by Van-Der-Waals interaction. The second one is the Hydrotalcite-like structure also called Layered Double Hydroxide (LDH) recognized by the following formula MII 1-x MIII x (OH)2 Ax. xH2O. The LDH regroups in the same layer a divalent and trivalent metals and are both arranged in the octahedral position2. The Simonkolleite-like structure3 (α-structure) with M1-x Oh Mx Td (OH)2-x Ax. yH2O as formula, is the third type which only contains divalent metals arranged in tetrahedral (Td) and octahedral (Oh) position.Layer double hydroxides are explored materials in the energy field. Multiple studies have been reported on the behaviour of the layered hydroxides materials in energy storage4 and conversion5. This material is very appealing for researchers worldwide due to their good electrochemical behaviour, chemical versatility, electrochemical stability, and their low cost as well6. For instance, LDHs based on earth-abundant elements are good candidates for electrode materials for oxygen evolution reaction (OER) in alkaline condition, as well as for supercapacitors. However, one of the major drawback of these materials is their low electrical conductivity, which represents a limitation in the optimization of the electrochemical performance and the assemble of devices.Among the different approximation to overcome this issue, we are intensively working on the modulation of the electronic properties of LHs. In this line, Co-based α-layered hydroxides, exhibiting simonkolleite-like structure, can be an interesting case of study since the covalent bond between the hydroxylated layer and the anion (figure 1). Indeed, we have recently demonstrated that the electrical properties can be modulated by halide substitution6, where the band gap can be reduced by ligand to metal charge transfer as demonstrated by DFT+U simulations. Considering these previous results, we decided to analyse the role of these chemical modifications in terms of the electrochemical properties.Interestingly, our results evidence a better electrochemical activity of Co-based α-LHs in comparison with the typical β-LHs or LDHs analogues, in both OER and specific capacitance performance7. Moreover, in the case of α-LHs the values can be further enhanced by tuning the nature of the anion: for instance, structures containing iodide overpass in more than 40% those ones containing chloride, as mentioned by DFT+U simulation (figure 2).Hence, this work positions α-CoII hydroxides as key phases among the layered hydroxides family as electrode materials for energy storage and conversion, where the conductivity can be improved by anion substitution8. 1 Brindley, G. W.; Kao, C.-C. Structural and IR Relations among Brucite-like Divalent Metal Hydroxides. Phys. Chem. Miner. 1984, 10 (4), 187–191. 2 Du, Y.; O’Hare, D. Synthesis, Morphology, Structure, and Magnetic Characterization of Layered Cobalt Hydroxyisocyanates. Inorg. Chem. 2008, 47 (8), 3234–3242. 3 Oestreicher, V.; Dolle, C.; Hunt, D.; Fickert, M.; Abellán, G. Room Temperature Synthesis of Two-Dimensional Multilayer Magnets Based on α-CoII Layered Hydroxides. Nano Mater. Sci. 2022, 4 (1), 36–43. 4 Zhang, D.; Cao, J.; Zhang, X.; Zeng, Z.; Insin, N.; Qin, J.; Huang, Y. Modification Strategies of Layered Double Hydroxides for Superior Supercapacitors. Adv. Energy Sustain. Res. 2022, 3 (3), 2100183. 5 Wang, Y.; Yan, D.; El Hankari, S.; Zou, Y.; Wang, S. Recent Progress on Layered Double Hydroxides and Their Derivatives for Electrocatalytic Water Splitting. Adv. Sci. 2018, 5 (8), 1800064. 6 Oestreicher, V.; Hunt, D.; Torres-Cavanillas, R.; Abellán, G.; Scherlis, D. A.; Jobbágy, M. Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations. Inorg. Chem. 2019, 58 (14), 9414–9424. 7 R. Sanchis-Gual, V. Oestreicher, G. Abellan et al. Submitted. 8 Y. Diouane, V.Oestreicher, G. Abellan et al, manuscript in preparation Figure 1

A single fluorescent chemosensor for detecting Ag+ ion in DMF and common trivalent metal ions in ethanol

A fluorescent chemosensor PAOP based on pyrene formaldehyde and o-phenylenediamine was successfully synthesized, and its molecular structure was characterized by NMR and mass spectrometry. PAOP exhibits excellent fluorescence sensing ability for Ag+ in DMF with high selectivity and sensitivity. In addition, PAOP can selectively identify common trivalent metal ions (Al3+, Fe3+, Cr3+) in ethanol solution. After the addition of common trivalent metal ions, the fluorescence of PAOP ethanol solution changed from blue–violet to blue–green. The results of the reversible fluorescence change, mass spectra, FT-IR and DFT calculations proved that the selective fluorescence response towards the special metal ions was attributed to formation of stable 2:1 complex PAOP@Mn+. PAOP has good recovery in detection of Cr3+ in real water samples and shows great potential application as a chemosensor.

Dual Monomeric Inorganic Units Constructed Bright Emissive Zero-Dimensional Antimony Chlorides with Solvent-Induced Reversible Structural Transition.

A5M2X11 and A3M2X9 families (A = monovalent organic cation; M = trivalent metal; X = halogen) are receiving increasing attention because of their combination of easy solution processability and superior ferroelectricity properties. However, synthesizing highly efficient A5M2X11 and A3M2X9-type fluorophores with multiple monomeric inorganic units and achieving their structural interconversion remains challenging. Here, we report two novel zero-dimensional (0D) antimony halides, (C10H16N)5Sb2Cl11·C2H3N (1) and (C10H16N)3Sb2Cl9 (2), which not only contain two distinct [SbXn]3-n units but also have excellent orange (590 nm) and yellow-green emission (540 nm) with high PLQY of 17.7% and 31.5%, respectively. Interestingly, a reversible structural conversion could be triggered by acetonitrile steam stimulation, accompanied by luminescence switching properties. This work not only enriches the structure of hybrid Sb-based halides but also provides the possibility of well-known A5M2X11 and A3M2X9 families as structural transformation materials.

Vibrational Coupling and Hydrogen-Bond Structure of Water in the Extended Hydration Shell of Metal Ions.

Intra- and intermolecular vibrational coupling (VC) and hydrogen bonding (H-bonding) of water are sparsely understood in the hydration shell (HS) of a metal ion, though the corresponding knowledge for an anion is quite extensive. This is primarily due to the overwhelming effect of anions on water, which masks the subtle perturbing influence of most of the cations. Using Raman difference spectroscopy with simultaneous curve fitting (Raman-DS-SCF) in combination with isotopic dilution and polarized Raman spectroscopy, we have elucidated the VC and H-bonding of water in the HS of bi- and trivalent metal ions─Mg2+, Ca2+, La3+, Gd3+, Dy3+. Polarized Raman measurement of the HS water with VC "turned on" and "turned off" (using isotopically diluted water, HOD) reveals that water retains the intra- and intermolecular vibrational coupling in the HS of high-charge-density metal ions, which is in stark contrast to that of an anion. Hydration shell spectroscopy in HOD unambiguously shows that the average H-bonding of water becomes stronger in the HS than that of bulk water. The first HS water strongly donates two H-bonds to the second HS water (ν̅max ≈ 3200 cm-1) but weakly accepts a H-bond from the second HS water (ν̅max ≈ 3590 cm-1), which makes the HS water heterogeneous in terms of its H-bond structure. The weakly interacting OH (ν̅max 3585 cm-1 in HOD) red-shifts by ∼ 15 cm-1 while the VC is "turned on" (ν̅max ≈ 3600 cm-1 in H2O), revealing the intramolecular coupling of water in the HS of metal ions.

Peroxymonosulfate activation by Ni-Fe (hydr)oxides through radical and nonradical pathways for efficient trichloroethylene degradation

Peroxymonosulfate (PMS)-based advanced oxidation processes have become promising water treatment technologies in recent years. The redox cycle between transitional metals in heterogeneous catalysis is essential for continuous activation of PMS and efficient removal of pollutants. In this work, we prepared Fe3O4 using precipitation method and subsequently added Ni aqueous solution to synthesize Ni-Fe (hydr)oxides. Ni-Fe (hydr)oxides show efficient PMS activation ability, causing the degradation of 96.8 % trichloroethylene (TCE) after 40 min with the dosage of Fe, Ni and PMS at 0.2, 0.1 and 0.2 mM, respectively. The catalyst concentration normalized TCE degradation rate constant of Ni-Fe (hydr)oxides/PMS system reaches 1.48 L g−1 min−1. Nonradical pathway is dominant at the initial stage of the reaction which generates high-valent metals, SO5•− and indirectly produces 1O2. 1O2 and dissolved O2 together participate in the O2 cycling, •OH generation, and electron transfer involving the reduction of trivalent metals. Divalent metals react with PMS to generate strong oxidative •OH and SO4•− through radical pathway in later stage. TCE is degraded and dechlorinated by multiple reactive species in Ni-Fe (hydr)oxides/PMS system. The optimum Ni/Fe ratio of catalysts under the studied conditions was 0.50. Ni-Fe (hydr)oxides show high reactivity and stability in real water matrices, demonstrating Ni-Fe (hydr)oxides are promising catalysts for PMS activation to degrade pollutants in contaminated water.

A Strategy for Tuning the Structure, Morphology, and Magnetic Properties of MnFe2O4/SiO2 Ceramic Nanocomposites via Mono-, Di-, and Trivalent Metal Ion Doping and Annealing.

This work presents the effect of monovalent (Ag+, Na+), divalent (Ca2+, Cd2+), and trivalent (La3+) metal ion doping and annealing temperature (500, 800, and 1200 °C) on the structure, morphology, and magnetic properties of MnFe2O4/SiO2 ceramic nanocomposites synthesized via sol-gel method. Fourier-transform infrared spectroscopy confirms the embedding of undoped and doped MnFe2O4 nanoparticles in the SiO2 matrix at all annealing temperatures. In all cases, the X-ray diffraction (XRD) confirms the formation of MnFe2O4. In the case of undoped, di-, and trivalent metal-ion-doped gels annealed at 1200 °C, three crystalline phases (cristobalite, quartz, and tridymite) belonging to the SiO2 matrix are observed. Doping with mono- and trivalent ions enhances the nanocomposite's structure by forming single-phase MnFe2O4 at low annealing temperatures (500 and 800 °C), while doping with divalent ions and high annealing temperature (1200 °C) results in additional crystalline phases. Atomic force microscopy (AFM) reveals spherical ferrite particles coated by an amorphous layer. The AFM images showed spherical particles formed due to the thermal treatment. The structural parameters calculated by XRD (crystallite size, crystallinity, lattice constant, unit cell volume, hopping length, density, and porosity) and AFM (particle size, powder surface area, and thickness of coating layer), as well as the magnetic parameters (saturation magnetization, remanent magnetization, coercivity, and anisotropy constant), are contingent on the doping ion and annealing temperature. By doping, the saturation magnetization and magnetocrystalline anisotropy decrease for gels annealed at 800 °C, but increase for gels annealed at 1200 °C, while the remanent magnetization and coercivity decrease by doping at both annealing temperatures (800 and 1200 °C).

Dependence relationship between doping modes and surface plasmon resonance properties of doped ZnO nanocrystals

The use of doped semiconductors to achieve plasmonic frequencies in the middle infrared (mid-IR) has been recently proposed as a promising way to obtain high-quality and tunable plasmonic materials. Plasmonic materials have great static or dynamic tunability. In some cases, choosing a dopant over another is an important trade-off to optimize the plasmonic performance. In this work, trivalent metal ion (M)-doped ZnO nanoparticles (NPs, M=Al, In) were successfully synthesized with highly consistent synthesis conditions. Interestingly, surface plasmon resonance (SPR) can only be observed in Al-doped ZnO (AZO) NPs, but not in In-doped ZnO (IZO) NPs. We used X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman and a first principle calculation to clarify the proper dopant sites (replaceable or interstitial doping) of Al3+ and In3+ in the host nanocrystals of ZnO. In addition, these results assisted by density of states (DOS) analysis indicate that different doping modes influenced the electronic structures in different degrees, and may lead to the opposite SPR phenomenon. Our work deepens the understanding of the relationship between doping sites in the host nanocrystals and SPR properties and give important guidance to the develop the doped semiconductors with plasmonic performance.

Competitive sorption behavior of mono, di, and trivalent ions in highly acidic waste by polymeric resin based on crotonic acid prepared by gamma radiation

Understanding the chemical behavior and interactions of mono, di, and trivalent metal ions in highly acidic solutions is very important in trying to predict their sorption process onto polymeric materials. In this work, the efficient polymeric resin has been prepared by gamma radiation approach during copolymerization synthesis of poly sodium styrene sulphonate and crotonic acid through systematic investigation. An installment of different parameters was constructed including polymer concentration, radiation dose, and how it affects equilibrium water content (EWC- swelling degree). The prepared polymer was characterized using Fourier Transform Infrared (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), Dynamic Light Scattering (DLS), and point of zero charges (pHZPC) analyses. The structure of such prepared co-polymeric resin analogous reaction was constructed. It was discovered that when the quantity of poly sodium styrene sulphonate increases, the copolymer forms more quickly and produces white crystalline materials. The sorption behavior of Fe3+, La3+ Ce3+, Eu3+, Sr2+ and Cs+ ions on the polymeric material was tested in a highly acidic aqueous solution taking into consideration the optimum solution pH, and initial metal concentration. The sorption ratio between different valence is challenging because of the competition of ion-specific, and binding saturation effects. Fortunately, in highly acidic waste, the synthesized polymeric resin exhibit higher removal efficiency for trivalent metal ions including Fe3+, Eu3+,Ce3+, and La3+ more than divalent Sr2+ and monovalent Cs+ ions with maximum sorption capacity 58, 56, 52, 48, 38 and 6.4 mg/g respectively. Finally, the synthesized polymeric resin P(SSS-Co-CA) is considered a promising sorbent for the selective separation of trivalent metal ions, especially in highly acidic solutions produced from acid digestion of real samples containing trivalent lanthanides.

Superstructures and Chemical Bonding in Rare Earth Metal Polytellurides RETe2‐δ (RE=La−Nd; Sm−Tm; 0≤δ≤0.2)

AbstractPolychalcogenides REX2‐δ (X=S, Se, Te; 0≤δ≤0.2) of trivalent rare earth metals RE have been investigated in recent years to shed light on the structural diversity as a function of compositional, metric, thermodynamic, and electronic situation. Whereas the former aspects have comparable influence on the structures of all polychalcogenides REX2‐δ, the bonding situation was assumed different for tellurides due to tellurium's higher tendency to delocalize electrons. The crystal structures generally contain puckered [REX] double slabs and planar [X] layers, the latter hosting different distortions from a square‐like arrangement. The distortion patterns of sulfides and selenides can be understood by a Zintl‐type approach; they are dominated by localization of valence electrons in mono‐ (X2−) or dinuclear (X22−) anions only. This review discusses crystal structures of some rare‐earth metal polytellurides RETe2‐δ (0≤δ≤0.2) and bonding features in the chalcogenide layers and relates them to their sulfide and selenide counterparts.

Metal Ion-induced Gelation of High-concentration Graphite-like Crystalline Nanosheet Aqueous Suspensions.

The stability and transformation of nanomaterial aqueous suspensions are essential for their applications. Preparation of high-concentration carbon nanomaterials suspensions remains challenging due to their nonpolar nature. Herein, 200mgmL-1 carbon nanomaterial aqueous suspensions are achieved by using graphite-like crystalline nanosheets (GCNs) with high hydrophilicity. Furthermore, these high-concentration GCN aqueous suspensions spontaneously transform into gels when induced by mono-, di-, and trivalent metal salt electrolytes at room temperature. Theoretical calculation of potential energy by DLVO theory reveals that the gelatinized GCNs is a new and metastable state between two usual forms of solution and coagulation. It is shown that the gelation of GCNs is due to the preferential orientation of nanosheets in an edge-edge arrangement, which differs from the case of solution and coagulation. High-temperature treatment of GCN gels produces metal/carbon materials with pore structures. This work provides a promising opportunity to create various metal/carbon functional materials.

Synthesis of magnetic electroactive nanomotors based on sodium alginate/chitosan and investigation the influence of the external electric field on the mechanism of locomotion

In this paper, we report a novel electric-driven Janus nanomotor (JNMs) based on SPIONs nanoparticle decorated with chitosan (Cs) and sodium alginate (Na/Alg) using the Pickering emulsion method. The JNMs dispersed in aqueous media exhibit linear trajectories under DC electric field, and the driving force is attributed to the self-electro-osmotic mechanism and surface modifications. This study offers an approach to remotely control the motion modes of the JNMs, including start, stop, directional and programmable motion, which can be advantageous for various application scenarios. The diffusion coefficient and velocity of the JNMs were investigated through mean square displacement analysis for single particle of JNMs, both in distilled water and in the presence of different di and trivalent metal cations (Fe3+, Al3+, Ba2+, Ca2+ and Mg2+) as crosslinking agents, as well as monovalent salts (LiCl and KCl). The results revealed that the motion of JNMs was fastest in the presence of Fe3+ as crosslinker agent (about 7.2181 μm2/s) due to its higher charge than equimolar Na+ . Moreover, it was demonstrated that increasing the ionic strength led to relatively higher speeds of JNMs, as the solution polarity increased and, as a result, the driving force of electro-osmoesis enhanced.

Effects of CaCl2 on the rheology, microstructure and protein structures of rapidly salted separated egg yolk

Bivalent or trivalent metal salts can enhance the oil output and sandiness of salted eggs. We added CaCl2 to the salting solution to improve the quality of rapidly salted separated egg yolk and investigated its effect on rheological, microstructure, and protein structure. According to the findings, adding CaCl2 to the salting solution can promote the precipitation of egg yolk water, increase its viscosity, induce protein aggregation, and increase the denaturation temperature of the protein. Scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) revealed that the inner boundary of egg yolk salted with CaCl2 was clearer and that the number and size of salted egg yolk lipoprotein aggregates were larger than those of egg yolk salted without CaCl2. Analysis using Fourier transform infrared spectroscopy (FTIR) demonstrated that CaCl2 caused the interconversion of the secondary-level structure. CaCl2 can have an impact on the microenvironment of amino acid residues, according to the results of 3D fluorescence and UV absorption spectra. Therefore, adding CaCl2 can accelerate the loss of water and change the structure of lipoprotein in egg yolk, which improves the sandiness and oil yield of salted separated egg yolk.

PH-Responsive Viscoelastic Fluids of a C22-Tailed Surfactant Induced by Trivalent Metal Ions.

pH-responsive viscoelastic fluids are often achieved by adding hydrotropes into surfactant solutions. However, the use of metal salts to prepare pH-responsive viscoelastic fluids has been less documented. Herein, a pH-responsive viscoelastic fluid was developed by blending an ultra-long-chain tertiary amine, N-erucamidopropyl-N, N-dimethylamine (UC22AMPM), with metal salts (i.e., AlCl3, CrCl3, and FeCl3). The effects of the surfactant/metal salt mixing ratio and the type of metal ions on the viscoelasticity and phase behavior of fluids were systematically examined by appearance observation and rheometry. To elucidate the role of metal ions, the rheological properties between AlCl3- and HCl-UC22AMPM systems were compared. Results showed the above metal salt evoked the low-viscosity UC22AMPM dispersions to form viscoelastic solutions. Similar to HCl, AlCl3 could also protonate the UC22AMPM into a cationic surfactant, forming wormlike micelles (WLMs). Notably, much stronger viscoelastic behavior was evidenced in the UC22AMPM-AlCl3 systems because the Al3+ as metal chelators coordinated with WLMs, promoting the increment of viscosity. By tuning the pH, the macroscopic appearance of the UC22AMPM-AlCl3 system switched between transparent solutions and milky dispersion, concomitant with a viscosity variation of one order of magnitude. Importantly, the UC22AMPM-AlCl3 systems showed a constant viscosity of 40 mPa·s at 80 °C and 170 s-1 for 120 min, indicative of good heat and shear resistances. The metal-containing viscoelastic fluids are expected to be good candidates for high-temperature reservoir hydraulic fracturing.

Dilution and packing of anionic liquid surfactant in presence of divalent and trivalent counter-ions

Alkyl ether carboxylates are part of a new class of ionic liquids based on the Concept of Melting Point Lowering due to Ethoxylation (COMPLET) and possess unique aggregation behaviour due to the simultaneous anionic and non-ionic nature of the surfactant anion. Previous publications on H[C8E8c] (Polyoxyethylene(8) octyl ether carboxylic acid) and its monovalent salts have shown a variety of phases in aqueous systems with a transition from small spherical micelles at high water contents towards a phase of interdigitated head groups at low water contents. In the present paper, we examine the shorter homologue H[C8E5c] (Polyoxyethylene(5) octyl ether carboxylic acid) and its di- and trivalent transition and rare earth metal salts using X-ray scattering methods in the small- and wide-angle range (SWAXS). These measurements confirm the presence of spherical micelles in diluted aqueous systems which aggregate and whose head groups interdigitate at higher concentrations of the isotropic, non-birefringent ionic liquid. Swelling experiments yield two-dimensional swelling of the microstructure, and combined with the scattering pattern, the data infer prolate spheroidal direct (o/w) micelles with interdigitated head groups, which align to form short linear chains. These chains are offset to form a localised hexagonal close-like packing of the micelles. Most interesting, within this packing, the metal cations are confined into channels between the micelles in linear chains with ion-ion distances of 0.4–1.1 nm. In particular, in the water-free ionic liquid, this confinement may be responsible for some of the unique properties of these systems. It is suggested that the confinement of the cations leads to strong ion-ion aggregation that could be at the origin of the very peculiar magnetic properties of these simple one-component liquids, which contrasts with classical ferrofluids, in which magnetic nanoparticles are dispersed in another liquid.

Induced Production of Atypical Naturally Nonpreferred Metal-Organic Frameworks and Their Detachment via Provoking Post-Mismatching.

The structures of metal-organic frameworks (MOFs) are typically determined by the building blocks that compose them and the conditions under which they are formed. MOFs tend to adopt a thermodynamically and/or kinetically stable structure (naturally preferred form). Thus, constructing MOFs with naturally nonpreferred structures is a challenging task, as it requires avoiding the easier pathway toward a naturally preferred MOF. Herein, an approach to construct naturally nonpreferred dicarboxylate-linked MOFs employing reaction templates is reported. Thisstrategy relies on the registry between the surface of the template and the cell lattice of a target MOF, which reduces the effort required to form naturally nonpreferred MOFs. Reactions of p-block trivalent metal ions (Ga3+ and In3+ ) with dicarboxylic acids typically produce preferred MIL-53 or MIL-68. However, the surface of UiO-67 (and UiO-66) template exhibits the well-defined hexagonal lattice, which induce the selective formation of a naturally nonpreferred MIL-88 structure. Inductively grown MIL-88s are purely isolated from the template via provoking a post-mismatch in their lattices and weakening the interfacial interaction between product and template. It isalso discovered that an appropriate template for effective induced production of naturally nonpreferred MOFs shall be properly selected based on the cell lattice of a target MOF.

Novel Pyrimidinethione Hydrazide Divalent and Trivalent Metal Complexes for Improved High-Performance Antimicrobial and Durable UV Blocking Cellulosic Fabric

Ultraviolet (UV)-protective and antimicrobial cotton fabrics are necessary for the protection of our skin. In this article, a pyrimidinethione hydrazide (PTH) derivative ligand was complexed with Mn, Co, Ni, Cu, Zn, and Cd as divalent metals and Fe and Cr as trivalent metals to prepare highly antimicrobial and UV-blocking metal–pyrimidinethione hydrazide-modified cotton fabrics (M-PTH-C). The cotton sample treated (M-PTH) was found to show improved efficiency over pyrimidinethione hydrazide-modified cotton (PTH-C). Cadmium-PTH-C showed the highest performance of antimicrobial action against Staphylococcus aureus (Gram-positive bacteria), Escherichia Coli (Gram-negative bacteria), and Candida albicans (fungi) with zones of inhibition 31 mm, 18 mm, and 27 mm, respectively. Furthermore, all M-PTH-C samples showed no effect against Candida albicans, except Co, Ni, and Cd pyrimidinethione hydrazide-modified cotton with inhibition zones of 16 mm, 27 mm, and 22 mm. In addition, no compounds showed any activity against Aspergillus flavus except Cd-PTH-C, which gave an excellent performance, with a 33 mm inhibition zone. Furthermore, most modified cotton fabrics have excellent UV protection. Fe-PTH-C showed 113.3 as the highest Ultraviolet protection factor (UPF) compared to the other modified samples. The tensile strength test of all samples was also investigated. The values of tensile strength for the treated cotton samples are slightly affected compared to the untreated ones.

Structural and Antimicrobial Investigation of Some New Nanoparticles Mixed Ligands Metal Complexes of Ethyl 6-Amino-4-(4-chlorophenyl)-5-cyano-2-methyl-4H-pyran-3-carboxylate in Presence of 1,10-Phenanthroline

A new series of some biologically active Cr(III), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) complexes was synthesized from the reaction of Ethyl 6-amino-4-(4-chlorophenyl)-5-cyano-2-methyl-4H-pyran-3-carboxylate (L) with the previous biological metals in the presence of 1,10-phenanthroline monohydrate (Phen). The structures of the obtained L along with their complexes were authenticated by different analytical and spectral techniques. The data prove that L chelates with all metal ions as bidentate through the nitrogen of the amino group and the nitrogen of the cyano group. Furthermore, Phen chelated with metal ions via two nitrogen atoms. The molar conductance values reflect that all complexes are electrolyte, confirming the 1:3 electrolytic natures for trivalent metal ions and 1:2 electrolytic for bivalent metal ions. The thermal stability and the general thermal decomposition pathways of metal complexes, L, and Phen were evaluating according to the thermogravimetric technique. The activation thermodynamic parameters were estimated from TG curves by utilizing Horowitz–Metzger (HM) and Coats–Redfern (CR) techniques. Powder X-ray diffraction (XRD) analysis proved that L, Cu(II), and Zn(II) compounds have a crystalline nature, whereas, Cr(III), Fe(III), Co(II), and Ni(II) complexes are semicrystalline. The investigated compounds were examined in vitro for their antimicrobial activity towards G(+ve) Staphylococcus aureus and Bacillus subtilis and G(−ve) Escherichia coli and Pseudomonas aeruginosa bacteria, and two fungi: Candida albicans and Aspergillus flavus. According to the findings, the Co(II) complex has a significant efficiency toward bacteria, additionally, Cr(III) complex is highly significant towards fungal strains.

Targeted Synthesis of an Highly Stable Aluminium Phosphonate Metal-Organic Framework Showing Reversible HCl Adsorption.

A concept for obtaining isoreticular compounds with tri- instead of tetravalent metal cations using highly acidic reaction conditions was developed and successfully applied in a high throughput study using N,N'-piperazinebis(methylenephosphonic acid) (H4PMP), that resulted in the discovery of a new porous aluminium phosphonate denoted CAU-60 ∙ 6 HCl. The high-throughput study was subsequently extended to other trivalent metal ions. Al-CAU-60 ∙ 6 HCl demonstrates reversible desorption of HCl (18.3 wt% loading) with three distinct compositions observed with zero, four or six HCl molecules per formula unit. Structural changes were followed in detail by powder X-ray diffraction, EDX analysis as well as IR spectroscopy. Rapid desorption of HCl in water within minutes and subsequent adsorption from the gas phase and from aqueous solution are shown. Furthermore, it is possible to adsorb HBr into the guest free Al-CAU-60 framework, demonstrating the high stability of this compound.

Targeted Synthesis of a Highly Stable Aluminium Phosphonate Metal–Organic Framework Showing Reversible HCl Adsorption

AbstractA concept for obtaining isoreticular compounds with tri‐ instead of tetravalent metal cations using highly acidic reaction conditions was developed and successfully applied in a high throughput study using N,N′‐piperazinebis(methylenephosphonic acid) (H4PMP), that resulted in the discovery of a new porous aluminium phosphonate denoted CAU‐60⋅6 HCl. The high‐throughput study was subsequently extended to other trivalent metal ions. Al‐CAU‐60⋅6 HCl demonstrates reversible desorption of HCl (18.3 wt % loading) with three distinct compositions observed with zero, four or six HCl molecules per formula unit. Structural changes were followed in detail by powder X‐ray diffraction, EDX analysis as well as IR spectroscopy. Rapid desorption of HCl in water within minutes and subsequent adsorption from the gas phase and from aqueous solution are shown. Furthermore, it is possible to adsorb HBr into the guest free Al‐CAU‐60 framework, demonstrating the high stability of this compound.

Study the metal impurities in potassium dihydrogen phosphate crystal by ion beam analysis

KDP (Potassium dihydrogen phosphate) crystal is one of the artificially grown crystals that has attracted the most attention. Now the fast growth method, which may easily introduce the metal impurities, is widely investigated. These metal impurity ions seriously affect growth rate and optical properties of the crystal. In this paper, the metal impurities Fe3+, Ba2+ and Cu2+ were doped into the growth solution of KDP crystals. The content and distribution of these metal impurities in KDP crystals were analyzed by a 3 MeV proton beam. The results indicate the chemical composition of elements O, K and P did not change by the impact from the ion beam. The limit of detection of Fe3+ was calculated. The results show that the trivalent metal ions in KDP crystals are easier to enter the crystals versus divalent ions and most of them distributed uniformly in the crystal.