Rapid growth of inch-sized lanthanide oxychloride single crystals
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Unusual Li2O sublimation promotes single-crystal growth and sintering
Li2O is rarely used for cathode material synthesis due to its high melting point (1,438 °C). Here we discover that Li2O can sublimate at 800–1,000 °C under ambient pressure, opening new possibilities for cathode synthesis. We propose a mechanism that enables synthesis of single crystals—such as LiNi0.8Mn0.1Co0.1O2 (NMC811) or LiNi0.9Mn0.05Co0.05O2 (NMC90)—without direct contact with Li2O salts. We show that Li2O vapour successfully converts spent polycrystalline NMC811 into segregated single crystals without milling or post-treatment. The Li2O vapour, derived from Li2O solids, diffuses rapidly and reacts with precursors, mimicking a molten-salt environment, which facilitates single-crystal growth. The chemical lithiation process continuously drives Li2O sublimation, sintering the crystals. Single crystals derived from Li2O and fresh precursors or spent polycrystals exhibit outstanding cycling after 1,000 cycles in full cells. The demonstrated Li2O sublimation and its universal role in promoting single-crystal growth provides an effective approach for single-crystal synthesis, scale-up and recycling.
Full-color tuning in multi-layer core-shell nanoparticles from single-wavelength excitation
Lanthanide-based luminescent materials have shown great capabilities in addressing scientific problems encountered in diverse fields. However, achieving full-color switchable output under single-wavelength irradiation has remained a daunting challenge. Here we report a conceptual model to realize this aim by the temporal control of full upconversion evolution in a multi-layer core-shell nanostructure upon a single commercial 980-nm laser, instead of two or more excitation wavelengths as reported previously. We show that it is able to realize the red-to-green color change (from Er3+) under non-steady state excitation by constructing the cooperative modulation effect in the Er-Tm-Yb triple system, and single out the blue light (from Tm3+) by filtering out the short-decay emissions via a time-gating technique. The key role of Tm3+ in manipulating up-transition dynamics of Er3+ is further demonstrated. Our results present a deep insight into the photophysics of lanthanides, and help develop new generation of smart luminescent materials toward emerging photonic applications.
Microscopic crystallographic analysis of dislocations in molecular crystals
Organic molecular crystals encompass a vast range of materials from pharmaceuticals to organic optoelectronics, proteins and waxes in biological and industrial settings. Crystal defects from grain boundaries to dislocations are known to play key roles in mechanisms of growth1,2 and in the functional properties of molecular crystals3,4,5. In contrast to the precise analysis of individual defects in metals, ceramics and inorganic semiconductors enabled by electron microscopy, substantially greater ambiguity remains in the experimental determination of individual dislocation character and slip systems in molecular materials3. In large part, nanoscale dislocation analysis in molecular crystals has been hindered by the low electron doses required to avoid irreversibly degrading these crystals6. Here we present a low-dose, single-exposure approach enabling nanometre-resolved analysis of individual dislocations in molecular crystals. We demonstrate the approach for a range of crystal types to reveal dislocation character and operative slip systems unambiguously.
Continuous 1D single crystal growth with high aspect ratio by oriented aggregation of dendrite
Continuous 1D growth of crystals is among one of the long-standing goals in material science. Classical generic methods for 1D crystal growth such as guided disposition restrict side growth by external bounding, and become difficult as the aspect ratio increases. Here, we find that continuous 1D growth of crystals can be achieved during dendrite formation, where the fractal dendrite crystal growth intrinsically restricts side broadening. We induce nanoparticle alignment in a solvent system with a polymer nanoparticle dispersion. This polymer additive further enabled an oriented aggregation mechanism during dendrite growth. The integration of these two mechanisms into the dendrite growth process regulates the dendrite shape. Such aggregated mono-crystalline dendrite branches can reach an ultra high aspect ratio (over 10000:1) with uniform diameter and orientation. We show an example application of such dendrite to prepare a high aspect ratio nanowire. This pathway may be extended for general 1D crystal growth system in the future.
Crystal structures of monomeric BsmI restriction endonuclease reveal coordinated sequential cleavage of two DNA strands
BsmI, a thermophilic Type IIS restriction endonuclease from Bacillus stearothermophilus, presents a unique structural composition, housing two distinct active sites within a single monomer. Recognition of the non-symmetrical 5’-GAATGC-3’ sequence enables precise cleavage of the top and bottom DNA strands. Synthetic biology interventions have led to the transformation of BsmI into Nb.BsmI, a nicking endonuclease. Here we introduce Nt*.BsmI, tailored for top-strand cleavage, which is inactive on standard double-stranded DNA, but active on bottom-strand nicked DNA, suggesting a sequential cleavage mechanism. Crystallographic structures of pre- and post-reactive complexes with cognate DNA show one major conformational change, a retractable loop possibly governing sequential active site accessibility. The x-ray structures reveal the position of the divalent metal ions in the active sites and the DNA:protein interactions, while the models predicted by Alphafold3 are incorrect. This comprehensive structural and functional study lays a foundation for rational enzyme redesign and potential applications in biotechnology.
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