CrystEngComm最新文献

A 3D metal–organic framework, designated UWDM-16, formula [Zn₆(μ₃-OH)₂(μ₂-RCO₂)₆(η¹-RCO₂)₄(η¹-RCO₂H)₂(H₂O)], with a (12)-c hexanuclear SBU was synthesized using a T-shaped [2]rotaxane linker and Zn(NO₃)₂·6H₂O under solvothermal conditions in DMF.

Electrochemical CO₂ reduction (eCO₂RR) provides a promising route for converting CO₂ into value-added carbon monoxide (CO), a key feedstock for chemical synthesis. Silver-based catalysts are among the most effective materials for this process; however, their practical development is often hindered by the poorly defined nature of their active sites, which limits precise structure–activity correlations. Herein, we report the synthesis of a structurally well-defined Ag⁺/Ti⁴⁺ bimetallic titanium-oxo cluster, Ti₆Ag₆, stabilized by thiacalix[4]arene ligands. The cluster adopts a distinctive linear architecture comprising three types of surface-exposed Ag sites. When applied to eCO₂RR, Ti₆Ag₆ exhibits outstanding catalytic performance, delivering over 90% faradaic efficiency for CO across a wide potential window. DFT calculations reveal that the central bridging Ag site exhibits the highest intrinsic activity, attributed to its superior ability to stabilize the *COOH intermediate.

Red-emitting phosphors activated by Mn⁴⁺ have gained increasing attention for applications in solid-state lighting and plant-growth illumination, owing to their excellent spectral match with both LED emission and the photosynthetically active radiation region. In this study, Mn⁴⁺-activated La₂MgSnO₆ phosphors were synthesized via a conventional high-temperature solid-state reaction, and Ge⁴⁺ was incorporated as a co-dopant to tailor their luminescent behavior. The samples exhibit a broad excitation band from 300 to 550 nm and a sharp red emission centered at 705 nm under 366 nm excitation. With increasing Ge⁴⁺ content, the emission intensity and quantum yield first increased and then decreased, reaching a maximum at 30 mol% Ge⁴⁺. At this composition, both fluorescence lifetime and thermal stability were significantly improved, while the emission wavelength remained nearly constant. These enhancements are attributed to Ge⁴⁺-induced local lattice modulation, which optimizes the coordination environment of Mn⁴⁺ ions, suppresses non-radiative losses, and facilitates radiative transitions. The results reveal that Ge⁴⁺ co-doping offers an efficient lattice-engineering strategy for improving the performance of Mn⁴⁺-activated La₂MgSnO₆ and provide valuable insight into the design of high-efficiency red phosphors.

The development of high-performance vanadium pentoxide (V₂O₅) cathodes is often constrained by the intricate synthesis of desirable nanostructures and an insufficient understanding of the synergistic impact of the morphology and dispersion on electrochemical properties. Herein, we report a facile solvothermal strategy for the controlled synthesis of V₂O₅ nanostructures, where the volume of hydrazine hydrate serves as the sole governing parameter for morphological evolution. By simply varying the hydrazine hydrate content, we successfully achieved the transformation from aggregated nanoparticles to dispersed nanorods and, optimally, to dispersed nanoparticles. When evaluated as cathode materials for lithium-ion batteries, the dispersed nanoparticles demonstrated superior electrochemical performance. They delivered high specific capacities of 254 and 130 mA h g⁻¹ at 0.2 C and 5 C, respectively, and exhibited excellent cyclability with 75% capacity retention after 100 cycles at 1 C. This enhanced electrochemical performance is attributed to the synergistic advantages of their dispersed morphology and nanoscale dimensions. This work provides profound insight into the structure–property relationship of V₂O₅ and offers a paradigm for the rational design of electrode materials for advanced energy storage systems.

Crystallization plays a vital role in pharmaceutical manufacturing by defining critical quality attributes such as purity, particle size, and polymorphic form. With the growing adoption of continuous manufacturing (CM) and increasing regulatory emphasis on process understanding, there is a clear need for systematic workflows that can ensure robust and reproducible crystallization outcomes. In this study, we develop and demonstrate a structured workflow for crystallization process design using imatinib mesylate, a high-value oncology drug that exists in two polymorphic forms. The approach integrates advanced process analytical technology (PAT) tools and offline characterization methods to characterize crystal properties, track phase transitions, and monitor process performance. A kinetically informed thermodynamic (KIT) design procedure is implemented through small-scale experiments to rank potential solvents not only by yield and polymorph control, but also by incorporating critical kinetic factors. Batch crystallization studies were used to identify key parameters influencing polymorph formation, which informed the design of a continuous crystallization process. The resulting process reproducibly produced the desired stable form, offering advantages in downstream handling and product quality. This case study illustrates how a stepwise, data-driven workflow can support polymorph selection and control, while enabling consistent performance in both batch and continuous crystallization systems. The proposed methodology contributes to the broader goals of modern pharmaceutical manufacturing, supporting quality-by-design (QbD) and continuous processing initiatives aligned with regulatory expectations.

NiCoFe-based multicomponent alloy catalysts have been extensively studied as non-precious metal high-entropy alloy catalysts. They exhibit outstanding electrochemical performance in the electrolytic hydrogen production process. Here, we employ one-dimensional carbon nanotubes as a substrate to prepare a series of carbon-based high-entropy heterostructure catalysts. The NiCoFeMnLa/CNTs@Cr₂O₃ composite structure is obtained by forming oxides on the surface via vapour deposition, effectively increasing the number of active sites. The carbon-based transition metal nanomaterial catalyst NiCoFeMnLa/CNTs@Cr₂O₃ exhibited outstanding performance in the alkaline electrolytic catalysis of the oxygen evolution reaction, achieving an overpotential of merely 235 mV at a current density of 10 mA cm⁻² in alkaline simulated seawater solution. Notably, the catalyst maintained relatively stable current density during 24 h electrochemical testing, indicating that the NiCoFe multicomponent alloy catalyst combined with Cr₂O₃ holds promise for enhanced stability during seawater electrolysis. Driven by these findings, this work may offer novel insights into the rational design of highly efficient electrocatalysts for green hydrogen production processes, particularly concerning carbon-based high-entropy alloy nanoparticle catalysts.

Metal–organic frameworks (MOFs), as a new class of porous heterogeneous materials, have been considered as a novel adsorbent material for CO₂ reduction in recent years due to their excellent adsorption capacity for CO₂, which is of great potential for development. In this paper, a Cd-containing metal–organic skeleton (AQNU-10) was successfully synthesized by adjusting the reaction temperature and solvent polarity using a semi-rigid polycarboxylic acid, H₃L, as a light-trapping organic ligand. It exhibited excellent photocatalytic performance, 128.81 μmol g⁻¹ for CO without adding any co-catalyst and photosensitizer, and could be stably recycled at least five times. The intrinsic mechanism of AQNU-10 in the photocatalytic CO₂ reduction process was explored through experimental characterization and testing.

Cs₃Cu₂I₅ is an ideal scintillator with excellent stability, high light yield and satisfying energy resolution. However, CsI inclusions can be easily formed during its growth, which are detrimental to its scintillation properties. This study successfully obtained Cs₃Cu₂I₅ single crystal with the vertical Bridgeman method. After the zone refining of raw material CuI, the formation of CsI inclusions can be effectively restrained. The observation of the inclusions by SEM demonstrated that they grow along the vertical direction of Cs₃Cu₂I₅. The origin of CsI inclusions can be explained by the constitutional supercooling theory. After the purification of CuI, the transmission of Cs₃Cu₂I₅ is significantly improved from 60% to 90%. Meanwhile, the light yield of the as-grown single crystal is increased from 34 860 ph MeV⁻¹ to 36 695 ph MeV⁻¹, and the energy resolution is also optimized from 6.7% to 4.0%.

Ground-level ozone is a typical atmospheric pollutant, making the development of efficient and stable ozone degradation technologies highly important. In this study, a self-exothermic reaction was utilized to successfully achieve kilogram-scale synthesis of nanocrystalline Cu₂O, using high-concentration ascorbic acid aqueous solution and solid Cu(OH)₂ as the precursors. Experimental results show that when the concentration of ascorbic acid is 0.77 mol L⁻¹, the obtained catalyst exhibits an ozone conversion rate of up to 98% at 25 °C at a high space velocity of 960 000 mL g⁻¹ h⁻¹, along with good moisture resistance and low-temperature stability. Furthermore, after processing the powder catalyst into a structured monolithic catalyst, the ozone removal rate remains above 92% at a high space velocity of 48 000 h⁻¹. Characterization analyses indicate that the high catalytic activity originates from the abundant defect structures and oxygen vacancies introduced during the self-exothermic synthesis process, which significantly increases the number of active sites. This study presents a simple and efficient method for large-scale production of high-performance Cu₂O catalysts, demonstrating broad application prospects in ozone pollution control.

The segregation of potassium ions during the growth of NBT-KBT (Na_(1−x)/2 Bi_0.5 TiO₃-K_x/2 Bi_0.5 TiO₃) single crystals via the high-temperature solution growth (self-flux) method is challenging. In this context, the present study performs potassium segregation in grown single crystals with varying potassium contents. The incorporation of low potassium content in the grown crystals is confirmed via elemental analysis. Further, a relationship between the initial sodium and potassium concentrations in the solute and their final compositions in the crystal is established. Moreover, the impact of potassium segregation on the structural, piezoelectric, dielectric and ferroelectric properties of the NBT-KBT single crystals is thoroughly investigated. To understand the impact of potassium substitution, structural transformations are analyzed using line profile analysis and Rietveld refinement. Near the morphotropic phase boundary (MPB), the simultaneous presence of rhombohedral and tetragonal phases is observed, leading to a synergistic enhancement of functional properties, such as piezoelectricity, dielectric permittivity, and ferroelectric polarization. Increasing the potassium concentration leads to a rise in the depolarization temperature, implying relatively strong resistance to thermal depolarization. Notably, near the MPB, the piezoelectric and ferroelectric properties reach their maximum, attributed to the structural phase coexistence and optimized domain configurations. Further, the Landau–Devonshire theory describes the temperature-dependent evolution of the ferroelectric behavior, where strong and stable polarization is observed at low temperatures. As temperature increases, domain stability weakens, leading to the emergence of ergodic relaxor characteristics, as reflected by relatively slim P–E loops. These results emphasize the importance of ionic size and domain evolution in enhancing the thermal stability and ferroelectric performance of lead-free NKBT piezoelectrics at the morphotropic phase boundary. These findings provide an effective approach for growing NBT-KBT single crystals with the desired composition and offer insights for optimizing lead-free piezoelectrics for sensor and actuator applications.