skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Titanium Oxysulfate‐Derived 1D Lepidocrocite Titanate Nanostructures
Abstract Nanostructured titania, TiO2, holds significant importance in various scientific fields and technologies for their distinctive properties and multipurpose characteristics. In this article, the facile, economical, and scalable synthesis of 1D lepidocrocite, 1DL, titania nanostructures derived from a water‐soluble Ti precursor, titanium oxysulfate (with oxidation of Ti+4) at temperature <100 °C under atmospheric pressure is discussed. Titanium oxysulfate with tetramethyl ammonium hydroxide, TMAH, is simply reacted to yield individual lepidocrocite titania‐based chain‐forming nanofilaments, NFs, 6 × 6 Å2in minimal cross‐section and aspect ratios of ≈20 1DLs. If only ethanol is used for washing, the 1DL self‐assemble into ≈10 µm, porous mesostructured particles, PMPs. If water is used, quasi‐2D sheets form instead. Characterization of the resulting powders showed them to be quite similar to those derived from TiB2, and other water‐insoluble Ti precursors. The 1DL bandgap energies are ≈4 eV, due to quantum confinement. They adsorbed rhodamine 6G. The latter also sensitized the 1DLs and allowed for dye degradation using only visible light. Used as electrodes in supercapacitors, the 1DLs can be cycled over 1.6 V and result in high power densities (300 W kg−1). Stronger birefringence started to appear in samples with concentrations >15 gL−1indicating the formation of a liquid crystal phase. This new synthesis protocol enables the cheaper scalable production of 1DLs with significant implications across various fields.  more » « less
Award ID(s):
2211319
PAR ID:
10585796
Author(s) / Creator(s):
; ; ; ; ; ; ; ;
Publisher / Repository:
Wiley
Date Published:
Journal Name:
Advanced Materials Interfaces
ISSN:
2196-7350
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract When a few drops of acid (hydrochloric, acrylic, propionic, acetic, or formic) are added to a colloid comprised of 1D lepidocrocite titanate nanofilaments (1DLs)–2 × 2 TiO6octahedra in cross‐section–a hydrogel forms, in many cases, within seconds. The 1DL synthesis process requires the reaction between titanium diboride with tetramethylammonium (TMA+), hydroxide. Using quantitative nuclear magnetic resonance (qNMR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC), the mass percent of TMA+after synthesis is determined to be ≈ 13.1 ± 0.1%. The TMA+is completely removed from the gels after 2 water soak cycles, resulting in the first completely inorganic, TiO2‐based hydrogels. Ion exchanging the TMA+with hydronium results in gels with relatively strong hydrogen bonds. The hydrogels' compression strengths increased linearly with 1DL colloid concentration. At a 1DL concentration of 45 g L−1, the compressive strength, at 80% deformation when acrylic acid is used, is ≈325 kPa. The strengths are ≈ 50% greater after the TMA+is removed. The removal of all residual organic components in the hydrogels, including TMA+, is confirmed by qNMR, Fourier‐transformed infrared spectroscopy (FTIR), and TGA/DSC. The 1DL phase is retained after gelation, TMA+removal, and 80% compression. 
    more » « less
  2. Lithium‐sulfur (Li‐S) batteries offer high specific capacities but their development is hindered by several issues, most notably polysulfide shuttle. Previously, a new form of titania nanomaterial, 1D lepidocrocite (1DL) nanofilaments was shown to serve as a sulfur (S) host for Li‐S batteries. In this work, porous mesostructured particles are introduced as a new morphology of the titania 1DL to improve its performance as a S host. Furthermore, employing a facile, aqueous, one‐step surface functionalization with dopamine enhances 1DL interactions with S, as confirmed by changes in infrared spectroscopy peaks and an increase in d‐spacing via X‐ray diffraction. This surface functionalization results in a reduction of 1DL band gap energy (Eg) from 3.62 to ≈2.29 eV, resulting in a 2.6‐fold increase in electrical conductivity. Additionally, the surface functionalization renders a more conformal coating of S on the 1DL, leading to increased S utilization and interaction with the 1DL. Electrochemical testing shows a 20% reduction in the polysulfide shuttle current in comparison to base 1DL and 560 mAh g−1at 0.5 C at a S‐loading of 2 mg cm−2. Postmortem X‐ray photoelectron spectroscopy analysis also reveals stronger thiosulfate signals in the dopamine‐functionalized 1DLs, further confirming improved S interactions compared to untreated 1DL. 
    more » « less
  3. Betz, Markus; Elezzabi, Abdulhakem Y (Ed.)
    Use of nanomaterials for photocatalysis faces challenges such as complex synthesis, high cost, low scalability, and dependance on UV radiation for initiating the photocatalytic activity. We recently demonstrated scalable, one-pot syntheses of one-dimensional (1D) lepidocrocite-based nanofilaments (NFs), 1DL NFs, that have the potential to overcome some of the challenges. 1DL NFs are exceptionally stable in water, have a large surface to volume ratio, and sub-square-nanometer cross sections. Initial reports show the semiconducting nature of this material, with an indirect band gap energy of 4.0 eV, one of the highest ever reported for a titania material. In this work, we present a study of the electronic and optical properties of these newly discovered 1DL NFs using ultrafast transient optical absorption. We show that despite the large band gap of this material, sub-gap states can be accessed with visible light illumination only, and photoexcited species reveal decay times in the nanosecond scale. Long lived photoexcitations in the visible range, without assistance by UV illumination, pave the way for possible application in photocatalysis. 
    more » « less
  4. One-dimensional lepidocrocite, 1DL, titania, TiO2, is a recently discovered form of this ubiquitous oxide that is of interest in a variety of applications ranging from photocatalysis to water purification, among others. The fundamental building blocks of these materials are snippets (30 nm long) of individual 1DLs that self-assemble into nanobundle, NB, structures. These NBs can then be driven to self-assemble into quasi-two-dimensional, 2D, sheets, films, or free-flowing mesoscopic particles. Here, we use analytical atomic-resolution scanning transmission electron microscopy (STEM) and first-principles density functional theory (DFT) calculations to demonstrate that the arrangement of the neighboring NFs can be altered through ion exchange with Li, Na, and tetramethylammonium hydroxide (TMA) cations. Moreover, using cryogenic electron energy-loss spectroscopy (EELS), we show that the introduction of different ion species results in a change in the local occupancy of the TiO2 t2g and eg orbitals. Both experimental findings are predicted by ground-state energy simulations of two-dimensional lepidocrocite TiO2. 
    more » « less
  5. Abstract Surface segregation is a ubiquitous phenomenon driven by minimization of the total free energy. In this paper we study surface segregation in multicomponent magnetic Bismuth ferrite nanoparticles alloyed with varying amounts of Dysprosium, Zinc and Titanium. We employ surface and bulk sensitive spectroscopic probes to unravel a significant surface segregation of Bismuth oxide and Titanium oxide. High coercive fields of BiFe0.95Ti0.05O3(BFTO) and BiFe0.96(Zn, Ti)0.02O3(BFZTO) at room temperature reveal that they have a strong exchange bias. This suggests that the Titanium oxide is magnetically active, and there is a Ti induceddoferromagnetism in action between these nanoparticles. We show, with the addition of Dy2O3, the Ti induceddoferromagnetism is suppressed making (BDFZTO) superparamagnetic. We observe that all three differently alloyed Bismuth ferrite nanoparticles show a non-saturating paramagnetic background. 
    more » « less