ABSTRACT Tri‐imidazole derivatives, widely recognized for their broad pharmacological and therapeutic activities such as antibacterial, anticancer, antidiabetic, antifibrotic, antifungal, anti‐inflammatory, antitubercular, and antiviral effect, used for efficiently synthesized using tetravalent metal acid (TMA) salts, which serve as heterogenous solid acid catalysts with stronger acidic sites, enhanced thermal stability, and improved selectivity in organic transformations. In this study, tri‐imidazole and its derivatives were synthesized under solvent‐free conditions using titanium phosphate (TiP), titanium‐amino trismethylene phosphonic acid (Ti‐ATMP), and titanium‐hydroxy ethylidene di‐phosphonic acid (Ti‐HEDP) as heterogenous solid acid catalysts. The catalysts were thoroughly characterized by PXRD, FT‐IR, SEM‐EDX, XPS, N 2 adsorption–desorption isotherms, NH 3 ‐TPD, and TGA analyses. A comparative investigation was conducted on the synthesis efficiency and recyclability of the catalysts, with progress monitored by TLC. Furthermore, a novel tri‐imidazole derivative was successfully synthesized and confirmed by melting point, NMR ( 1 H, 13 C and 19 F) spectral analysis.

Acetate salts, owing to their low cost and high safety, show promise as supporting electrolytes for aqueous batteries. Building on the "water-in-salt" (WiS) strategy, recent studies propose using mixed cations to increase total salt concentration, thereby optimizing the electrochemical stability window (ESW) and battery performance. In this study, various Na-K binary acetate aqueous solutions were investigated, and their phase transition behaviors at room temperature were first reported, analyzed through thermal and electrochemical characterizations. When applied in a full-cell system (sodium manganese hexacyanoferrate/sodium titanium phosphate), the 16 mol kg-1 potassium acetate +8 mol kg-1 sodium acetate exhibited a matching ESW and better interface features than higher-concentration alternatives, making it more suitable for aqueous batteries. It maintained a specific capacity of 32 mAh g-1 after 500 cycles. These findings highlight the importance of multidimensional considerations for WiS electrolytes to meet application requirements.

The structure of titanium phosphate glasses (TiO2)x(P2O5)1-x with 0.70 ≤ x ≤ 0.75 was investigated by combining neutron and high-energy x-ray diffraction with solid-state 31P nuclear magnetic resonance (NMR) and Raman spectroscopy. The results were interpreted with the aid of an analytical model that delivers the composition dependence of the structural motifs. The structure of these materials was also simulated using abinitio molecular dynamics. A detailed 31P magic-angle spinning (MAS) NMR lineshape analysis, aided by the results obtained from double-quantum coherence spectroscopy, indicates the presence of P-O-P-connected network forming units at a level decreasing from 23% to 11% with increasing x. The diffraction results show a Ti-O coordination number of 5.32(7) at x = 0.715 that increases to 5.49(7) at x = 0.750. The findings demonstrate the prevalence of five- and six-coordinated titanium atoms and the coexistence of both two-coordinated oxygen atoms, O(II), and three-coordinated oxygen atoms, O(III). The Ti-centered polyhedra contribute to a network in which the phosphate groups form P-O(II)-Ti and P-O(III)-2Ti connections, with signatures that are evident in the 31P MAS NMR spectra. The results suggest that structural variability is a key factor in promoting vitrification in this atypical glass-forming system. The findings provide a benchmark for investigating the structure of other glass-forming materials based on networks of higher-coordinated polyhedral units.

The development of environmentally benign catalysts for the valorization of CO2 remains a crucial challenge in sustainable chemistry. In this work, we report a nitrogen-enriched acid-base bifunctional titanium phosphate catalyst (CC-3A-TiP), synthesized via intercalation of layered α-TiP with aminosilanes and cyanuric chloride. The resulting material features dual active sites, including Lewis acidic centers (Ti4+, -OH) and Lewis basic functionalities (-NH-, -C═N-), which facilitate the cooperative activation of epoxides and CO2 molecules. Comprehensive structural and spectroscopic characterization confirmed the presence and accessibility of these active sites. The synergistic acid-base interactions enabled highly efficient catalytic performance, achieving >99% conversion, 99% yield, and 100% selectivity toward cyclic carbonates under mild, solvent-free conditions, remarkably, without the use of halogenated cocatalysts such as TBAB, commonly employed in conventional systems. The catalyst demonstrated excellent stability and recyclability, maintaining ∼92% yield over five consecutive cycles. A plausible mechanism involving direct cycloaddition of epoxide and CO2 without any cocatalyst was proposed, highlighting the intrinsic bifunctional nature of the catalyst. DFT studies confirm that the bifunctional nature of the catalyst, offering both acidic and basic sites, drastically lowers the activation energy to 7.21 kcal mol-1, much lower than literature values, highlighting its vital role in facilitating CO2 cycloaddition with epoxides, which is further supported by experimental kinetics showing an activation energy of 9.06 kcal mol-1 in excellent agreement with the DFT results. The cocatalyst-free and solvent-free operational profile, along with high activity and recyclability, underscores the potential of CC-3A-TiP for sustainable CO2 conversion applications.

Improved adsorption of rare earth La3+ by monovalent salts (Na, K, and NH4) modified titanium phosphate (TiP) materials

Towards high-performance solid-state lithium batteries via antimony doping solid electrolytes.

Enhanced desalination performance in asymmetric flow electrode capacitive deionization with sodium titanium phosphate and Bi electrodes

Abstract Titanium phosphate (TiP) exhibits significant potential for the removal of U(VI) from aqueous solutions. In this study, tetra-n-butyl titanate (TBOT) and phosphoric acid were employed as titanium and phosphorus sources, respectively, and the P/Ti ratio was varied during the hydrothermal synthesis. Both amorphous and α-type TiPs were successfully synthesized, and their physicochemical properties at different P/Ti ratios were characterized using XRD, FTIR, SEM, zeta potential, and TG analysis. The effects of pH and P/Ti ratio on adsorption performance were systematically investigated, revealing that all TiPs achieved maximum adsorption capacity at pH 7.0. The adsorption behavior conformed to the Langmuir model, with a theoretical maximum adsorption capacity of 266.4 mg g −1 at a P/Ti ratio of 2. In the presence of multiple competing ions, amorphous TiP demonstrated higher selectivity for U(VI) compared to α-type TiP. Mechanistic studies indicated that U(VI) adsorption primarily occurs via surface complexation and ion exchange processes on the TiP surface. Overall, the adsorption efficiency of U(VI) can be effectively optimized by adjusting the P/Ti ratio in TiP.

Achieving high metal leaching efficiency via regulation strategy is essential for minimizing raw material waste and reducing waste generation in hydrometallurgy. However, conventional approaches of tuning temperature and time frequently result in increased equipment corrosion and increased industrial costs. Therefore, recycling waste solid-state battery relies on the development of new tuning strategies. Here, a new strategy is developed to tune the leaching efficiency of metals by amino acid-based low-melting mixture solvents from lithium aluminum titanium phosphate Li1.3Al0.3Ti1.7P3O12 (LATP) in all-solid-state lithium-ion batteries. This novel strategy demonstrates a more pronounced metal leaching efficiency, resulting in an increase in the highest Li leaching efficiency from 48.0% to 78.2%. In comparison, tunability by solvent types, temperature, and time on Li efficiency is less efficient, with Li efficiency only varying from 44.9% to 52.3%, 37.7% to 51.0%, and 36.8% to 56.3%, respectively.

Study of the Structural, Conductivity and Mobility Mechanism on the Incorporation of Zr4+ Ions in Lithium Titanium Phosphate Electrolytes for Lithium Batteries

Experimental study of the thermal behavior of potassium-magnesium-zirconium(titanium) phosphates with the langbeinite structure

Mussel-inspired surface-engineering of 3D printed scaffolds employing bedecked transition metal for accelerated bone tissue regeneration.

Titanium compounds, especially oxides and oxyanionic salts, have received considerable attention as lithium- or sodium-based battery anode materials that offer faster and safer operations at potentials with enough margin down to those of metal deposition. Among them, titanium phosphates possess a wide variety of framework structures that can host intercalant guest ions. Here, we report electrochemical Li+ intercalation properties of a titano phosphate oxide hydrate, ρ-Ti2O(PO4)2·2H2O, in non-aqueous and hydrate-melt electrolytes. The reactions occur at ca. 2.42 V vs Li/Li+ with a bi-phasic phase evolution up to α ∼ 1 in ρ-Li α Ti2O(PO4)2·2H2O, where lithium ions are in a space forming large tunnels coordinated by phosphates and crystal water. Applying conventional dilute-salt aqueous electrolytes with large water activity led to quick capacity decay due to the electrode instability issues caused by dissolution and hydrogen evolution.

This study investigates the potential of LAITP/PVDF composite electrolytes to improve the safety and performance of lithium-ion batteries. The study focuses on the synthesis and characterization of composite solid electrolyte consisting of indium-doped lithium aluminum titanium phosphate (LAITP) ceramic material and LiClO4 salt with polyvinylidene fluoride (PVDF) as the polymer matrix. The LAITP ceramic, synthesized via solid-state synthesis, demonstrates high ionic conductivity, thermal stability, and mechanical robustness. PVDF provides electrochemical and thermal stability to the composite. The composite electrolytes were prepared by integrating LAITP into the PVDF matrix through the solution casting method. Various characterization methods were employed to assess the properties of the resulting composite. X-ray diffraction (XRD) was used to examine the crystal structure, while scanning electron microscopy (SEM) provided insights into the morphological features. Ionic conductivity measurements were conducted using electrochemical impedance spectroscopy (EIS), enabling an evaluation of the composite's electrochemical performance. The LAITP-reinforced PVDF-based composite solid electrolyte exhibited an ionic conductivity of 1.7 × 10⁻5 S cm⁻1 at room temperature.

Poly(vinyl chloride) (PVC) undergoes thermal degradation during processing and operation, which necessitates the use of effective thermal stabilizers. The purpose of this work is to comprehensively evaluate the potential of new hierarchically structured titanium phosphates (TiP) with controlled morphology as thermal stabilizers of plasticized PVC, focusing on the effect of morphology and Ti/P ratio on their stabilizing efficiency. The thermal stability of the compositions was studied by thermogravimetric analysis (TGA) in both inert (Ar) and oxidizing (air) atmospheres. The effect of TiP concentration and its synergy with industrial stabilizers was analyzed. An assessment of the key degradation parameters is given: the temperature of degradation onset, the rate of decomposition, exothermic effects, and the carbon residue yield. In an inert environment, TiPMSI/TiPMSII microspheres demonstrated an optimal balance by increasing the temperature of degradation onset and the residual yield while suppressing the rate of decomposition. In an oxidizing environment, TiPR rods and TiPMSII microspheres provided maximum stability, enhancing resistance to degradation onset and reducing the degradation rate by 10–15%. Key factors of effectiveness include ordered morphology (spheres, rods); the Ti-deficient Ti/P ratio (~0.86), which enhances HCl binding; and crystallinity. The stabilization mechanism of titanium phosphates is attributed to their high affinity for hydrogen chloride (HCl), which catalyzes PVC chain scission, a catalyst for the destruction of the PVC chain. The unique microstructure of titanium phosphate provides a high specific surface area and, as a result, greater activity in the HCl neutralization reaction. The formation of a sol–phosphate framework creates a barrier to heat and oxygen. An additional contribution comes from the inhibition of oxidative processes and the possible interaction with unstable chlorallyl groups in PVC macromolecules. Thus, hierarchically structured titanium phosphates have shown high potential as multifunctional PVC thermostabilizers for modern polymer materials. Potential applications include the development of environmentally friendly PVC formulations with partial or complete replacement of toxic stabilizers, the optimization of thermal stabilization for products used in aggressive environments, and the use of hierarchical TiP structures in flame-resistant and halogen-free PVC-based compositions.

Revisiting lithium aluminium titanium phosphate chemistry: Unveiling advancements for all-solid-state batteries

Nano-titanium dioxide ceramic coatings exhibit excellent wear resistance, corrosion resistance, and self-cleaning properties, showing great potential as multifunctional protective materials. This study proposes a synergistic reinforcement strategy by encapsulating micron-sized Al2O3 particles with nano-TiO2. A core-shell structured nanocomposite coating composed of 65 wt% nano-TiO2 encapsulating 30 wt% micron-Al2O3 was precisely designed and fabricated via a slurry dip-coating method on Q235 steel substrates. The microstructure and surface morphology of the coatings were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD). Comprehensive performance evaluations including densification, adhesion strength, wear resistance, and thermal shock resistance were conducted. Optimal coating properties were achieved under the conditions of a binder-to-solvent ratio of 1:15 (g/mL), a heating rate of 2 °C/min, and a sintering temperature of 400 °C. XRD analysis confirmed the formation of multiple crystalline phases during the 400 °C curing process, including titanium pyrophosphate (TiP2O7), aluminum phosphate (AlPO4), copper aluminate (Cu(AlO2)2), and a unique titanium phosphate phase (Ti3(PO4)4) exclusive to the 2 °C/min heating rate. Adhesion strength tests revealed that the coating sintered at 2 °C/min exhibited superior interfacial bonding strength and outstanding performance in wear resistance, hardness, and thermal shock resistance. The incorporation of nano-TiO2 into the 30 wt% Al2O3 matrix significantly enhanced the mechanical properties of the composite coating. Mechanistic studies indicated that the bonding between the nanocomposite coating and the metal substrate is primarily achieved through mechanical interlocking, forming a robust physical interface. These findings provide theoretical guidance for optimizing the fabrication process of metal-based ceramic coatings and expanding their engineering applications in various industries.

Sodium titanium phosphate (NaTi2(PO4)3, NTP) has emerged as a promising electrode material due to its three‐dimensional open framework. This study investigates the use of NTP in aqueous dilute Li+/Na+ electrolytes and extends its application to high‐concentration K+ electrolytes. X‐ray photoelectron spectroscopy, X‐ray absorption near‐edge structure analysis, and density functional theory calculations revealed that highly electronegative fluorine partially substitutes for oxygen in the NTP lattice, resulting in the formation of Ti‐F bonds. The substitution effectively modulates the electronic structure of Ti4+, alters the local coordination environment, and influences the redox dynamics. Enhanced long‐term cycling stability and rate performance were demonstrated across aqueous sodium‐ion, lithium‐ion, and potassium‐ion half‐cells. Among the investigated systems, the aqueous sodium‐ion system exhibited the best electrochemical performance, characterized by a single, well‐defined charge–discharge plateau, stable cycling behavior with 88.7% capacity retention after 500 cycles at 1 A g−1, and an initial specific discharge capacity of 121.7 mAh g−1 at 0.2 A g−1. The results establish F‐doped NTP as a promising candidate for advanced energy storage applications in aqueous alkali metal‐ion batteries.

NASICON-type titanium and zirconium phosphates doped with rare-earth cations, A0.33M2(PO4)3 (M = Ti, Zr; A = Dy, Y, Yb), were synthesized using the sol–gel method and investigated as catalysts for ethanol dehydration at 300–400 °C. The catalysts were characterized via XRD, SEM, BET, and FTIR spectroscopy. The relationships between the catalyst composition, acidity and the dehydration activity were evaluated. Diethyl ether (DEE) formation is promoted by the presence of the zirconium phosphates (ZrP), while the presence of titanium phosphate (TiP) catalyzes the formation of both ethylene and diethyl ether (DEE). The application of Fourier-transform infrared (FTIR) spectroscopy to the analysis of adsorbed C6H6 has revealed the presence of hydroxyl groups exhibiting varying degrees of proton-donating mobility. This finding has enabled the correlation of the structure of the active sites with the process’s selectivity. The results underscore the key function of OH-group localization and framework geometry in the control of form-selective reactions.

Advancements in ionic devices for energy applications (e.g., solid-state microbatteries, ionic capacitors, ion-tunable transistors, etc.) require significant development of compatible materials and fabrication processes to enable high-performance conduction and storage of ions. Atomic layer deposition (ALD) enables fabrication of solid-state devices with high energy and power densities due to the complex structures made possible by its angstrom-scale thickness control and high conformality. The ionic conductivity of thin film materials fabricated by ALD has been limited by material development and crystallinity control challenges, as suitable materials must be fabricated with both the appropriate composition and crystal structure. A mixed metal phosphate like LiTi2(PO4)3 (LTP) is a prime candidate to push the boundary of ALD ionic materials due to the fast Li+-conducting NASICON-type crystalline phase. We developed a mixed ion-electron conducting NASICON-type thin film ALD process for LiTi2(PO4)3 suitable for microbattery and pseudocapacitor applications. Compositional tunability was achieved by alternating between constituent lithium oxide (Li2O) and titanium phosphate (TiPO) subprocesses. By adjusting the ratio between Li2O and TiPO cycles, the Li content in LTP can be tuned between 8 and 34 atomic % Li. A NASICON-type crystalline structure is observed after postdeposition annealing of the LTP films between 650 and 850 °C. The semicrystalline LTP thin film has an ionic conductivity of 9.3 × 10-7 S/cm at RT and 1.7 × 10-5 S/cm at 80 °C and an electronic conductivity of 2.5 × 10-7 S/cm at RT. In this work, we discuss the complexities of how tuning the composition of LTP influences film properties such as structure and conductivity in the mixed metal phosphate phase space.