The development of anode materials with high-rate capability is critical to high-power lithium batteries. T-Nb 2 O 5 has been widely reported to exhibit pseudocapacitive behavior and fast lithium storage capability. However, the other polymorphs of Nb 2 O 5 prepared at higher temperatures have the potential to achieve even higher specific capacity and tap density than T-Nb 2 O 5 , offering higher volumetric power and energy density. Here, micrometer-sized H-Nb 2 O 5 with rich Wadsley planar defects (denoted as d-H-Nb 2 O 5 ) is designed for fast lithium storage. The performance of H-Nb 2 O 5 with local rearrangements of [NbO 6 ] octahedra blocks surpasses that of T-Nb 2 O 5 in terms of specific capacity, rate capability, and stability. A wide range variation in the valence of niobium ions upon lithiation was observed for defective H-Nb 2 O 5 via operando X-ray absorption spectroscopy. Operando extended X-ray absorption fine structure and ex situ Raman spectroscopy analyses reveal a large and reversible distortion of the structure in the two-phase region. Computation and ex situ X-ray diffraction analysis reveal that the shear structure expands along major lithium diffusion pathways and contracts in the direction perpendicular to the shear plane. Planar defects relieve strain through perpendicular arrangements of blocks, minimizing volume change and enhancing structural stability. In addition, strong Li adsorption on planar defects enlarges intercalation capacity. Different from nanostructure engineering, our strategy to modify the planar defects in the bulk phase can effectively improve the intrinsic properties. The findings in this work offer new insights into the design of fast Li-ion storage materials in micrometer sizes through defect engineering, and the strategy is applicable to the material discovery for other energy-related applications.
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Local structure analysis and structure mining for design of photocatalytic metal oxychloride intergrowths
In this work, the local structures of durable, high-activity Bi 4 TaO 8 Cl–Bi 2 GdO 4 Cl intergrowth photocatalysts that were prepared in a molten flux are determined by pair distribution function analysis of X-ray total scattering data and correlated to their photocatalytic performance. This system gives understanding to how the local structure of photocatalysts can be manipulated controllably through incorporation of rigid and flexible layers via intergrowth formation to achieve high activity. This analysis revealed that the local symmetry and distortion of the [TaO 6 ] octahedra introduced through intergrowth formation and dictated by intergrowth stoichiometry correlate with their photocatalytic activity. That is, the greater the Ta–O–Ta bond angles, the higher the photocatalytic activity of a given intergrowth for the oxygen evolution reaction. Moreover, greater tilting of the [TaO 6 ] octahedra is associated with a larger band gap. This analysis was coupled with a structure mining approach to model the intergrowth structure by building supercells for refinement of the X-ray diffraction data. This analysis found that Ta- and Gd-domains are separated within the intergrowths, with large Gd-domains separated by small Ta-domains at high Gd% and the opposite for high Ta%. Taken together with Williamson–Hall analysis, our results highlight that the local structure of layered materials can be modulated through strain engineering enabled by the selection of rigid and flexible intergrowth layers, providing a new design pathway to high performance photocatalysts.
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- NSF-PAR ID:
- 10418751
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 10
- Issue:
- 43
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 23212 to 23221
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Bi2NiMnO6(BNMO) epitaxial thin films with a layered supercell (LSC) structure have emerged as a promising single‐phase multiferroic material recently. Because of the required strain state for the formation of the LSC structures, most of the previous BNMO films are demonstrated on rigid oxide substrates such as SrTiO3and LaAlO3. Here, the potential of BNMO films grown on muscovite mica substrates via van der Waals epitaxy, spotlighting their suitability for cutting‐edge flexible device applications is delved. Comprehensive scanning transmission electron microscopy/energy‐dispersive X‐ray analyses reveal a layered structure in the BNMO film and a pristine interface with the mica substrate, indicating high‐quality deposition and minimal interfacial defects. Capitalizing on its unique property of easily cleavable layers due to weak van der Waals forces in mica substrates, flexible BNMO/mica samples are fixed. A standout feature of the BNMO film grown on mica substrate is its consistent multiferroic properties across varied mechanical conditions. A novel technique is introduced for thinning the mica substrate and subsequent transfer of the sample, with post‐transfer analyses validating the preserved structural and magnetic attributes of the film. Overall, this study illuminates the resilient multiferroic properties of BNMO films on mica, offering promising avenues for their integration for next‐generation flexible electronics.
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Abstract Solar photocatalysis is a potential solution to satisfying energy demand and its resulting environmental impact. However, the low electron–hole separation efficiency in semiconductors has slowed the development of this technology. The effect of defects on electron–hole separation is not always clear. A model atomically thin structure of single‐unit‐cell Bi3O4Br nanosheets with surface defects is proposed to boost photocatalytic efficiency by simultaneously promoting bulk‐ and surface‐charge separation. Defect‐rich single‐unit‐cell Bi3O4Br displays 4.9 and 30.9 times enhanced photocatalytic hydrogen evolution and nitrogen fixation activity, respectively, than bulk Bi3O4Br. After the preparation of single‐unit‐cell structure, the bismuth defects are controlled to tune the oxygen defects. Benefiting from the unique single‐unit‐cell architecture and defects, the local atomic arrangement and electronic structure are tuned so as to greatly increase the charge separation efficiency and subsequently boost photocatalytic activity. This strategy provides an accessible pathway for next‐generation photocatalysts.
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Amorphous magnetic alloys with large perpendicular magnetic anisotropy (PMA) have emerged as a suitable material choice for spintronic memory and high-frequency non-reciprocal devices on-chip. Unlike ferromagnets, ferrimagnets offer faster switching dynamics, lower net saturation magnetization, minimal stray field and a lower net angular momentum. Ferrimagnetic thin films of Gd x Co 1− x sputter deposited as heterostructures of Ta/Pt/Gd x Co 1− x (t)/Pt on Si/SiO 2 have bulk-like PMA for thicknesses of 5–12 nm and room-temperature magnetic compensation for x = 28–32%. Preferential oxygenation of GdCo has been found to increase the effective anisotropy energy density by an order of magnitude and produce near-ideal remanence ratios. X-ray photoelectron spectroscopy accurately quantifies the metal-oxidation ratio, which shows that an oxygen-rich and Co-deficient stoichiometry (Gd 21 Co 28 O 51 ) likely weakens the ferromagnetic exchange interaction between Co–Co and contributes additional antiferromagnetic exchange through superexchange-like interactions between Gd and Co via O, resulting in a stronger out-of-plane magnetization. Even greater PMA and giant-anisotropy field of 11 kOe are achieved in super-lattices of the Gd 21 Co 28 O 51 heterostructure. The combination of ferrimagnetic ordering in amorphous Gd x Co 1− x and its affordance of pathways for engineering large PMA will enable the design of integrated high-frequency devices beyond 30 GHz and ultrafast energy efficient memory devices with switching speeds down to tens of picoseconds.more » « less
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Abstract Bor1p is a secondary transporter in yeast that is responsible for boron transport. Bor1p belongs to the SLC4 family which controls bicarbonate exchange and pH regulation in animals as well as borate uptake in plants. The SLC4 family is more distantly related to members of the Amino acid‐Polyamine‐organoCation (APC) superfamily, which includes well studied transporters such as LeuT, Mhp1, AdiC, vSGLT, UraA, SLC26Dg. Their mechanism generally involves relative movements of two domains: a core domain that binds substrate and a gate domain that in many cases mediates dimerization. To shed light on conformational changes governing transport by the SLC4 family, we grew helical membrane crystals of Bor1p from
Saccharomyces mikatae and determined a structure at ∼6 Å resolution using cryo‐electron microscopy. To evaluate the conformation of Bor1p in these crystals, a homology model was built based on the related anion exchanger from red blood cells (AE1). This homology model was fitted to the cryo‐EM density map using the Molecular Dynamics (MD) Flexible Fitting method and then relaxed by all‐atom MD simulation in explicit solvent and membrane. Mapping of water accessibility indicates that the resulting structure represents an inward‐facing conformation. Comparisons of the resulting Bor1p model with the X‐ray structure of AE1 in an outward‐facing conformation, together with MD simulations of inward‐facing and outward‐facing Bor1p models, suggest rigid body movements of the core domain relative to the gate domain. These movements are consistent with the rocking‐bundle transport mechanism described for other members of the APC superfamily.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2TA05663A
