Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K45/00—Medicinal preparations containing active ingredients not provided for in groups A61K31/00 - A61K41/00
  • A61K45/06—Mixtures of active ingredients without chemical characterisation, e.g. antiphlogistics and cardiaca
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G23/00—Compounds of titanium
  • C01G23/04—Oxides; Hydroxides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
  • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present disclosure relates to the field of ID and 2D materials and to the field of metal oxide-based nanomaterials.
• the resulting flakes are C-containing anatase-based layers that are in turn comprised of ⁇ 6 xlO A 2 nanofilaments (in some embodiments) in cross-section some of which are few microns long. Electrodes made from some of these films performed well in lithium-ion and lithium-sulphur systems. These materials also reduce the viability of cancer cells thus showing potential in biomedical applications.
• the present disclosure provides a composition, comprising: a plurality of metal oxide (e.g., metal oxide-based) nanofilaments and/or subnanofilaments, and optionally an amount of carbon.
• the nanofilaments can comprise titanium.
• Example such compositions are found in “Bottom-up, scalable synthesis of anatase nanofilament-based two- dimensional titanium carbo-oxide flakes”, Badr et ak, Materials Today (2021), the entirety of which is incorporated herein by reference for any and all purposes.
• a device comprising a composition according to the present disclosure, e.g., according to any one of Aspects 1-16.
• compositions comprising a population of anatase nanoparticles made according to the present disclosure, e.g., according to one of Aspects 38-42.
• a method comprising: contacting a mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal with a quaternary ammonium salt and/or base, the mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal optionally being non-water-soluble, the non-water soluble binary, or ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide optionally comprising a transition metal, the transition metal optionally comprising titanium, the contacting optionally performed while shaking, and the contacting being performed under conditions sufficient to give rise to mesoporous particles.
• a method comprising: contacting a mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal with a quaternary ammonium salt and/or base, the mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal optionally being non-water-soluble, the non-water soluble binary, or ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide optionally comprising a transition metal, the transition metal optionally comprising titanium, the contacting optionally performed while shaking, the contacting being followed by washing with at least one salt and performed under conditions sufficient to give rise to mesoporous particles.
• a method comprising: contacting a mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal with a quaternary ammonium salt and/or base, the mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal optionally being non-water-soluble, the non-water soluble binary, or ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide optionally comprising a transition metal, the transition metal optionally comprising titanium, the contacting performed while shaking and at a temperature of from about 50 to about 95 °C, followed by washing with LiCl to give rise to mesoporous particles.
• mesoporous particles made according to the present disclosure, e.g., according to any one of Aspects 45-47.
• compositions comprising mesoporous particles, wherein the mesoporous particles comprise titanium and wherein the mesoporous particles exhibit a XRD pattern that, when compared to a XRD pattern of nano- or bulk anatase, exhibit reduced (104) and (105) peaks at around 38° and about 55° two theta (2Q).
• a method comprising effecting delivery of a therapeutic to a subject, the therapeutic comprising in a composition according to the present disclosure, e.g., according to any one of Aspects 48-49.
• a method comprising effecting delivery of a therapeutic to a subject, the therapeutic comprising in a composition according to the present disclosure, e.g., according to any one of Aspects 48-49.
• an electrode comprising a composition according to the present disclosure, e.g., according to any one of Aspects 48-49.
• a device comprising a composition according to the present disclosure, e.g., according to any one of Aspects 48-49.
• FIGs. 1A-1D Fabrication process, scanning electron microscope (SEM) micrographs and Density functional theory (DFT) structures.
• FIG. 1A Schematic of fabrication process
• FIG. IB Typical cross-sectional SEM micrograph of a TiC-derived filtered film (FF). Note undigested TiC particles in bottom right comer. Inset shows pictures of typical colloidal suspension.
• FIG. 1C Isometric side view of 4 Ti-layered 2D anatase-based structure with TbCLC chemistry that best fits XRD and selected area diffraction (SAD) results. Blue, orange, red, and black spheres represent Ti, 2- and 3-fold coordinated O, and C respectively.
• FIG. ID Top view of nanofilaments (nfs) growing in [200] (top) and [110] (bottom) directions.
• Inset in (FIG. ID) compares experimental LPs (dashed lines) with DFT predictions (solid lines) as a function of number of Ti layers. Our coordinate system is shown in lower left in c and d and is not that of bulk anatase.
• FIGs. 2A-2D Characterization of 2D material.
• FIG. 2A XRD patterns, on log scale, of filtered, vertically oriented, TbAlC2-derived film in transmission mode. Inset shows pattern of horizontally oriented film. 5° 2Q peak is due to Kapton tape. Blue squares are 2Q locations determined from TEM-SAD patterns (Table 3).
• FIG. 2B Raman spectrum of FF obtained from precursors indicated. All powders heated at 50 °C for 3 d and washed with ethanol and water, except the top T1B2 one that treated at 80°C for 2d. All peaks belong to anatase. [15] (FIG.
• FIG. 3A Typical transmission electron microscope (TEM) image of TCO flake > 4 pm in lateral size. SAD of area encircled in red is shown in top right inset. Two arcs indicate fiber texture along [110] and [200] directions. Bottom inset is a higher magnification of top left comer showing frayed nanofilaments in a direction that is in accordance with the arcs.
• FIG. 3B Scanning transmission electron microscope (STEM) showing individual filaments, the width of which is ⁇ 10 A. Bottom inset shows nanofilaments being chemically "drawn out" from a large central T13AIC2 particle.
• FIG. 3C Atomic force microscope (AFM) of TCO self-assembled nanofilaments derived from TiC heated in TMAH at 80°C for 3d and washed with water.
• FAM Atomic force microscope
• FIGs. 5A-5F SEM micrographs of FFs’ cross sections after ethanol and LiCl washing made starting with, (FIG. 5A) Ti3SiC2, (FIG. 5B) T13AIC2, (FIG. 5C)
• TriSbP (FIG. 5D) TiN, (FIG. 5E) T1B2, and (FIG. 5F) TriSri. Insets show corresponding colloidal suspensions and FFs.
• FIGs. 6A-6C X-ray diffractograms (shifted vertically for clarity) of FF from
• FIG. 6A Parent TiC, T13AIC2, TriSiC2 precursors (black lines), and their derived 2D TCO films (red, blue, and green curves, respectively) after washing with ethanol and without sonication.
• FIG. 6B TiC (red, bottom), T13AIC2 (blue, middle), and TriSiC2 (green, top) derived films after washing with ethanol then LiCl solution.
• FIG. 6C T1B2 (red, bottom), TiN (blue, middle), and TriSri (green, top), derived films after washing with ethanol then LiCl solution.
• FIG. 7A Setup used to obtain XRD patterns from vertically oriented films in transmission mode. Inset shows Kapton tape with drop cast film taped to vertical aluminum sample holder.
• FIG. 7B XRD patterns (shifted vertically for clarity) of vertically aligned ethanol washed FF, derived from precursors indicated.
• TMAH TMAH
• TiC powders were immersed in the TMAH at 50°C for lid (blue, top).
• XRD characterization 1-1.5 ml of colloidal suspension was drop cast on Kapton tape using a pipette then air dried. Black vertical line at 5° originated from the Kapton tape. Blue lines are guides to the eye to the anatase-based 2D structure.
• FIGs. 8A-8F Typical TEM images of (FIG. 8A) and (FIG. 8B) TiC- derived flakes (50 °C, 3d) (FIG. 8C) Same as (FIG. 8A) but TiC was heated to 80°C for 3d emphasizing the fibrous nature of our TCO flakes.
• FIG. 8D nanofilaments crystallizing from an amorphous TCO background. Inset reveals high resolution image of crystalline nanofilaments 2-3 nm wide and few microns long. In the previous cases, reaction products were water washed.
• FIG. 8E Ti3SiC2-derived flakes (50°C for 3d, washed with ethanol) captured from crushed FF.
• FIG. 8F Nanofilaments appearing to be chemically “drawn” from T13AIC2 phase (dark particle in center) (50°C, 3d; washed with ethanol and water). Insets show SAD pattern from area bounded by red circles. Inset in f show both faint rings (from TCO) and MAX phase spots.
• FIG. 10A 6-layered anatase structure.
• Slab thickness is ⁇ 8 A.
• FIG. 10B Phonon density of states of 4-layered structure shown in Fig. lc.
• Fig. 11 Post LiCl-washed XPS spectra of Ti 2p region (1 st column), C Is region (2 nd column), O Is region (3 rd column) and Fermi edge (4 th column) obtained from TiC- (1 st row, top) , T13AIC2- (2 nd row), Ti3SiC2- (3 rd row), TiN- (4 th row), T1B2- (5 th row), and TiCh-based (6 th row) films. Peak fits and results are summarized in Tables 4 and 7. Dashed vertical lines are guides to the eye. [0035] Figs. 12A-12B.
• XPS spectra as a function of processing in Ti 2p region (1 st column), C Is region (second column), O Is region (third column), and Fermi edge (last column) of, (FIG. 12A) T13AIC2 -based and, (FIG. 12B) TriSiC2 -based filtered films. Dashed vertical lines are guides to the eye. Notably positions of Ti peaks appear to be insensitive to solution used to wash the films and even after heating to 800 °C in Ar in the T13AIC2 case (compare top spectra in blue to those below them in a).
• FIGs. 13A-13E XPS spectra of TCO FF for (FIG. 13A) N Is and, (FIG. 13B) Cl 2p regions derived from TiC (black, bottom), T13AIC2 (red, second from bottom) Ti3SiC2(blue, third from bottom), TiN (green, third from top), T1B2 (purple, second from top) and T1O2 (yellow, top) powders, (FIG. 13C) Si 2p spectra the Ti3SiC2-derived FF, (FIG. 13D) A12p spectra for Ti3AlC2-derived FF, (FIG. 13E) B is spectra for T1B2- derived FF. All samples were washed with ethanol and LiCl before filtration, followed by vacuum drying before XPS analysis.
• FIG. 14A Thermogravimetric plots for, (FIG. 14A) All samples, ramped at 10 °C/min to 800 °C in Ar. Sample labeled ethanol was washed with ethanol; those labeled LiCl were first washed with ethanol and then with a LiCl solution. (FIG. 14A)
• Fig. 15 Rietveld analysis of XRD diffractograms of LiCl washed filtered films heated to 800 °C in Ar. The c 2 values are listed on figures. Results are summarized in Table 8. Purple lines are differences between fits in red and experimental results in black.
• FIG. 16A XRD diffraction patterns of TiCh-derived material heated in TMAH for times and temperatures indicated on figure. In the 2D anatase the (104 and (105) peaks are absent and the 63° peak is shifted towards 60°.
• FIG. 16B TEM of anatase nanoparticles in the range of 20 nm. Insets show high magnification image and SAD pattern of the obtained T1O2 nanoparticles.
• FIGs. 17A-17D Electrochemical performance of Ti3AlC2-based TCO as electrode materials in Li-ion battery.
• FIG. 17A Electrochemical impedance spectroscopy Nyquist plot at open circuit potential
• FIG. 17B Specific capacity vs. cycle number and specific currents indicated.
• FIG.17C Voltage profile at specific current of 100 mA g 1 .
• FIG. 17D Specific capacity and Coulombic efficiency vs. cycle number for cell shown in c.
• FIGs. 18A-18B Electrochemical characterization of TiC-based FF electrode in Li-S cell: (FIG. 18A) CV curves, (FIG. 18B) Cycling stability at 0.2 C. S- loading is 0.8 mg. Capacity was, more or less, constant at ⁇ 1000 mAh/g for about 300 cycles before fading.
• Fig. 19 provides images of exemplary mesoscopic materials according to the present disclosure.
• Table 1 provides sources of example powders and reagents used in this work.
• Table 2 provides a summary of example precursors, TkTMAH mole ratios, and synthesis conditions.
• Table 3 provides a summary of interlayer spacing (d) values and the corresponding diffraction angle (2Q) acquired from XRD pattern shown in Fig. 2a and their comparison to those obtained from 7 different SAD patterns obtained from 5 different samples. All samples derived from parent TiC heated at 50°C then washed with ethanol and water.
• Table 4 provides a summary of fitting of XPS results shown in Fig. 11.
• Table 5 provides chemistries of 5 different flakes deduced from EELS measurements shown in Fig. 2c. Last row suggests possible chemistries where X sum of O, C and N. Flakes were prepared by dry rubbing filtered films made by heating TiC powders in TMAH for 3d at 50°C, then washed with ethanol.
• Table 6 provides chemistries of number of flakes from different precursors deduced from EDS measurements. Last row suggests possible Ti:0 ratios of these samples.
• SEM-EDS measurements were obtained from cross-sections of filtered films made of the precursor T13AIC2, Ti3SiC2, Ti3GaC2 powders reacted with TMAH at 50°C for 72h and washed with ethanol then a LiCl solution.
• TEM-EDS measurements were conducted on samples prepared by dry rubbing Ti3SiC2- and TiB2-derived filtered films made by reacting the powder with TMAH at 50°C for 72h and washing with ethanol.
• Table 7 provides Ti:0 chemistries obtained from the Ti area under ⁇ 459 eV peak and O under ⁇ 530 eV peak shown in Fig. 11.
• Table 8 provides a summary of Rietveld analyses of filtered films after heating in Ar to 800°C. Corresponding XRD patterns are plotted in Fig. 15.
• the term “comprising” can include the embodiments “consisting of and “consisting essentially of.”
• the terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named ingredients/steps and permit the presence of other ingredients/steps.
• compositions or processes as “consisting of and “consisting essentially of the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any impurities that might result therefrom, and excludes other ingredients/steps.
• the terms “about” and “at or about” mean that the amount or value in question can be the value designated some other value approximately or about the same. It is generally understood, as used herein, that it is the nominal value indicated ⁇ 10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
• an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where “about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
• approximating language can be applied to modify any quantitative representation that can vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially,” may not be limited to the precise value specified, in some cases. In at least some instances, the approximating language can correspond to the precision of an instrument for measuring the value.
• the modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4” also discloses the range “from 2 to 4.” The term “about” can refer to plus or minus 10% of the indicated number.
• compositions that comprises components A and B can be a composition that includes A, B, and other components, but can also be a composition made of A and B only. Any documents cited herein are incorporated by reference in their entireties for any and all purposes.
• TMAH acts as a near-universal solvent that dissolves the precursor and releases Ti atoms that spontaneously react with C and O in the TMAH/water to form 2D flakes comprised of self-assembled nanofilaments (see below).
• the TMAH role is thus twofold: solvent and templating agent.
• a X-ray diffraction (XRD) pattern of a Ti3AlC2-derived film after ethanol washing is typical of 2D materials.
• XRD patterns of dry FF obtained from other precursors are shown in Fig. 6. The absence, for the most part, of peaks associated with the precursors is noteworthy.
• Fig. 2a X-ray diffraction
• the red vertical lines were obtained as follows: First, the c-lattice parameter, LP, was calculated from horizontally oriented film (inset in Fig. 2a). The structure shown in Fig. lc was then used to calculate the position of all peaks. All planes with non-zero t indices were eliminated, leaving the red lines. The good agreement between the density functional theory (DFT) generated LPs and the experimental ones (inset in Fig. Id) lends credence that we are dealing with a 4 Ti-layered anatase-based 2D material (see below). Patterns for other vertically oriented films, derived from other precursors, are shown in Fig. 7b. In all cases, peaks - with identical angles - were obtained. This is crucial and cannot be overemphasized since it demonstrates that precursor chemistry does not alter the structures formed, including their LPs.
• DFT density functional theory
• One set of arcs indicated that the long axis of the nanofilaments is in the [110] direction; the other in the [200] direction. The angle between them is shown in both inset and main micrograph. They are in the same directions as the frayed fibers seen at the sheet edges in top left.
• the scanning transmission electron microscope (STEM) micrograph (Fig. 3b) clearly shows the fibrous nature of the sample.
• the width of individual nanofilaments is estimated to be ⁇ 1 nm. Since their thickness is ⁇ 5.9 A, it follows that we are dealing with nanofilaments roughly 6 xlO A 2 in cross-section that can be micrometers long (see inset in Fig 3b and Fig. 8c).
• Other TEM micrographs are shown in Fig. 8. We note in passing theoretical surface area of these nanofilaments is ⁇ 1500 m 2 /g.
• Figure 3c and Figure 9 show TEM and atomic force microscope (AFM) maps of a TiC-derived sample (5d at 80°C, water washed), spin coated on glass. The fibrous nature of the product and its tendency for self-alignment are obvious.
• AFM atomic force microscope
• the LPs of the b axes of the three structures are in good agreement with experimental values especially given that the DFT calculations were performed at 0 K.
• a large increase in the a-LP is observed - that is closer to the experimental values - when the number of Ti layers increases to 4 or 6 (blue curves in inset in Fig. Id).
• the thicknesses of the 4- and 6-layered anatase are - 5.9 A and ⁇ 8 A. respectively.
• the diameter of a TMA cation ranges from 4.5-6 A [17, 18] Using the low end, the ri-spacing between filaments for the 4- and 6-layered structures would be 10.4 A and 12.5 A, respectively.
• Fig. 8d is a snapshot of how, in certain regions, the nanofilaments self-align to form "crystalline" regions.
• Films derived from TiC and the MAX phases were conductive, with conductivities in the range of 0.01 to 0.05 S/cm; those made with T1O2 and T1B2 are not. These conductivities are roughly 5 to 6 orders of magnitude lower than MXenes, that range from 2,000 to 25,000 S/cm, but notably orders of magnitude higher than typical oxides, especially the more common version of layered titanates, viz. lepidocrocites.[23- 25] The conductivity is not always present and suggests an unknown variable is at play that is currently being investigated.
• Li-S Lithium sulfur
• an additional step of washing with LiCl solution was conducted and the produced flakes were characterized.
• a 5M LiCl solution was added to the black colloidal suspension obtained above. This resulted in deflocculation.
• the sediment was shaken and rinsed with deionized water through centrifugation at 5000 rpm for three cycles.
• the LiCl/DI water washing process was repeated until the pH was - 7.
• the washed sediment was then sonicated in a cold bath for 1 h under flowing Ar, shaken for 5 min, then centrifuged at 3500 rpm for 10 min.
• the colloidal suspension was filtered to produce FFs. The FFs were then left to dry in a vacuum chamber overnight before further characterization.
• the black slurry - produced from the reaction of TMAH and TiC - centrifuged (at 5000 rpm for 5 min) directly without the addition of any solvents, the supernatant decanted, the sediment resuspended in 20 mL DI water, shook for 5 min, then centrifuged at 3500 rpm for 30 min.
• the produced black colloidal suspension was used for XRD (not shown) and TEM inspection.
• the yield was calculated as fraction of the number of moles of Ti in the produced anatase-like structure (molar mass of TiCh is used for simplicity) to those supplied by the precursor. For instance, the yields for TiC and T13AIC2 are 19% and 28%, respectively. In general, the yield is of the order of - 20% depending on starting precursor.
• the solid loading in our colloidal suspensions is of the order of 10 g/L.
• XRD patterns on air dried samples were acquired using a powder diffractometer (Rigaku SmartLab) setup in the Bragg-Brentano geometry with Cu Ka radiations in the 2-65° 2Q range using a 0.02° step size and a dwell time of 1 s/step.
• Raman scattering spectra were collected at 300 K in air from FF of a number of precursors (Fig. 2b). The samples were probed using a 532- nm laser emitting 3.75 mW of power at the sample and focused to a spot diameter of -0.5 pm. Scattered light was collected in a backs cattering geometry and was dispersed and detected using a single-axis monochromator equipped with a charge-coupled detector array (Horiba XploRA, Edison NJ)
• XPS was performed using a spectroscope (VersaProbe 5000, Physical Electronics, Chanhassen, Minnesota). Monochromatic Al-Ka X-rays with a 200 pm spot size were used. A pass energy of 23.5 eV, with an energy step of 0.05 eV and a step time of 0.5 s was used to gather high-resolution spectra. Number of repeats per scan was 10. XPS spectra were calibrated by setting the major C-C peak to 285.0 eV. Peaks were fit using asymmetric Gaussian/Lorentzian line shapes. The background was determined using the Shirley algorithm. All samples were mounted on a XPS stage using carbon tape.
• Thicknesses of filaments and flakes were obtained with an AFM (Multimode 8 AFM from Bruker Nano Surfaces). A peak force tapping AFM imaging mode was applied to acquire the surface morphology and height profiles. The scanning was conducted with ScanAsyst-Air Silicon Nitride Probes at a scan rate of 0.6 Hz. Topographic images were recorded as the resolution of 256*256 pixels and analyzed by Nano Scope Analysis software.
• TEM imaging and electron diffraction patterns were collected using a JEOL JEM2100F field-emission TEM.
• the TEM was operated at 200 keV and has an image resolution of 0.2 nm.
• Images and diffraction patterns were collected on a Gatan USC1000 CCD camera.
• Scanning transmission electron microscopy, STEM was carried out in the monochromated and double Cs corrected FEI Titan3 60-300 operated at 300 kV.
• STEM-EELS spectra were acquired by averaging 100 spectra, acquired for 1 s each at a 0.25 eV/channel energy dispersion, and collection semi-angle of 55 mrad of employed Gatan GIF Quantum ERS post-column imaging filter. Elemental quantification of present edges was performed using built in functions of Digital Micrograph. [00103] X-ray absorption near edge structure, XANES
• the Ti K-edge isotropic XANES spectra were recorded at 54° from the normal to the film using circularly polarized x-rays provided by the first harmonic of the HELIOS-II type helical undulator (HU-52).
• the x-ray beam was monochromatized using a fixed-exit double crystal monochromator equipped with a pair of Si(l 11) crystals.
• Total fluorescence yield signal was collected by a Si photodiode mounted in back-scattering geometry. Spectra were corrected for self-absorption effects.
• the samples were ⁇ 1 mm thick compressed powered pellets.
• the isotropic XANES spectra were normalized to an edge jump of unity far above the absorption edge.
• the photon energy scale was calibrated using the pre-peak maximum in the absorption spectrum of a Ti thin foil that was set to 4965.6 eV. Spot size was 0.4x0.3 mm 2 . Experiments were performed at European Synchrotron Radiation Facility (ESRF) ID12 beamline in Grenoble
• thermobalance (TA Instruments Q50, New Castle DE) was used for the TGA analysis. Small pieces of FF ( ⁇ 20 mg) were heated in sapphire crucible at 10 °C/min, under purging Ar at 10 mL/min, to 800 °C. In one experiment we used a thermobalance attached to a mass-spectrometer. In these measurements a thermal analyzer (TA instruments, SDT 650, Discovery Series) coupled with a mass spectrometer (TA instruments Discovery Series) operating at 40 V ionizing potential was used. Samples were held at RT for 0.5 h then heated to 800°C at 10°C/min under dry compressed air flow at 50 mL/min. The carrier gasses and evolved gas products from the sample were measured by scanning over the 1-100 atomic mass unit range. The ion current for each m/z (mass/charge ratio) was normalized by the initial sample weight.
• UV-VIS spectra were recorded using spectrophotometer (Evolution 300 UV -Visible, Thermo Scientific). Measurements were performed in transmission mode on 1-1 Opm thick films coated onto quartz slides. [00111] DFT calculations
• the electronic configurations of the pseudopotentials used were C: [He]2S 2 2P 2 , O: [He]2s 2 2p 4 and Ti_sv: [Ne]3s 2 3p 6 3d 2 4s 2 .
• the calculation supercells were constructed to consist of various anatase (101) atomic layers using a slab model, with periodicity along the a and b axes of the supercell, which correspond to the [100] and [101] directions of bulk anatase, respectively.
• the supercell geometry and atom positions were relaxed until the force on each atom ⁇ 5 meV/A.
• a vacuum region of 15 A was added along the oaxis (in new coordinate system) of the supercell to eliminate interactions between periodic images perpendicular to the slabs.
• the first Brillouin zone was sampled by a 16x6x1 k-point sampling, while a 8x3x1 supercell together with a 2x2x1 k-point sampling was used for the phonon
• TCO electrochemical performance of TCO as electrode material as LIB material
• the TCA working electrodes were fabricated by drop-casting a slurry of active materials with binder and carbon additive on a carbon coated copper foil.
• the slurry was prepared by mixing 40.0 mg of active materials, 5.0 mg of poly(vinylidene fluoride) (PVDF, Sigma Aldrich, US) binder in N-methyl-2-pyrrolidinone (NMP, 99.5%, Acros Organics, Extra Dry over Molecular Sieve, Germany) solvent, and 5.0 mg of carbon black.
• PVDF poly(vinylidene fluoride)
• NMP N-methyl-2-pyrrolidinone
• the as-prepared electrodes were dried overnight at 60 °C.
• the electrode mass loading was ⁇ 1.2- 1.5 mg/cm 2 .
• Two-electrode CR2032-type coin cells were assembled in an Ar-filled glovebox with O2 and H2O ⁇ 0.1 ppm. Li metal foil was used as a counter electrode. 1M L1PF6 in ethylene carbonate (EC)/ ethyl methyl carbonate (EMC) with 3:7 (by weight) and glass fibers were used as electrolyte and separator, respectively.
• CV and galvanostatic charge- discharge testing were performed with a cut-off electrochemical voltage window of 0.001- 3.0 V vs Li/Li + using an electrochemical workstation (BioLogic VMP3) and a cycler (Landt CT2001A,). Electrochemical impedance spectroscopy with frequency from 100 kHz to 10 mHz were conducted in a electrochemical workstation (BioLogic VMP3).
• TCO/S cathodes using a slurry-based method. Briefly, the slurry was prepared by mixing 35 wt% vacuum-dried TCOs, 35 wt% sulphur, S, with 20 wt% conductive carbon (Alfa Aesar, Super P) and 10 wt.% battery grade PVDF binder (MTI Corp., USA). The materials were hand-ground with a mortar and pestle until the mixture appeared uniform. Later, N-Methyl-2-pyrrolidone (TCI, USA) was slowly added until the required visible consistency and uniformity of the slurry were achieved ( ⁇ 25 minutes).
• TCI N-Methyl-2-pyrrolidone
• the slurry was later cast on aluminum foil using a doctor blade (MTI Corp., USA) with a thickness of 20 pm. Once cast, the slurry was kept in a closed fume hood for 2 h before transferring to a vacuum oven where it was dried at 50 °C for 12 h.
• the dried TCO/S cathodes were cut using a hole punch (diameter 11 mm) to form disks.
• the electrodes were then weighed and transferred to an Ar-filled glove box (MBraun Lab star, O2 ⁇ 1 ppm, and H2O ⁇ 1 ppm).
• the CR2032 (MTI Corporation and Xiamen TMAX Battery Equipment) coin-type Li-S cells were assembled using TCO/S cathodes, a 15.6 mm diameter, 450 pm thick Li disk anode (Xiamen TMAX Battery Equipment) a tri-layer separator (Celgard 2325), and a stainless-steel spring and two spacers along with the electrolyte.
• the electrolyte with 1 M LiTFSi with 1 wt% L1NO3 in a mixture of 1,2-dimethoxy ethane and 1,3-dioxolane at a 1:1 volume ratio, was purchased (TMAX Battery Equipment, China) and according to manufacturer contained trace amounts of oxygen and moisture (H2O ⁇ 6 ppm and O2 ⁇ 1 ppm). Assembled coin cells were rested at their open-circuit potential for 10 h before performing the electrochemical experiments at RT. Cyclic voltammetry was performed at a scan rate of 0.1 mV.s 1 between voltages 1.8 and 2.6 V wrt Li/Li + using a potentiostat (Biologic VMP3).
• the Li-S cells were conditioned for 2 cycles at 0.1 C and 0.2 C, before undergoing long cycling at 0.5 C.
• the TEM images show that the aligned regions are a fraction of the total. In a sizable fraction, the nanofilaments are not aligned, but randomly oriented in the plane of the flakes. This has also been confirmed by selected area diffraction pattern (SAD) that showed diffraction rings for most of the characterized flakes.
• SAD selected area diffraction pattern
• FIG. 2c The EELS spectra on 5 different particles were measured on TiC-based flakes obtained after heating in TMAOH for 3d at 50 °C and ethanol washed.
• Figure 2c includes carbon -K edge at -280 eV energy loss, titanium -L3,2 peaks at -450 eV energy loss and oxygen -K edge at -530 eV energy loss. All spectra are normalized to the Ti edge peak intensity. Thicker particles exhibit a steeper background, which is more easily seen at the low energy of the spectrum. The top and bottom spectra exhibit a pronounced lower intensity compared to the three particles in the middle.
• the top and bottom spectra contain approximately the same amount of C, while for the three in the middle (2, 3 and 4) the chemistry was consistent aTi:C:0 atomic ratio of- 1:1:1. All spectra also show a minor amount of N-K (not shown) at -400 eV energy loss. For the remainder of this paper, this small amount of N will be ignored.
• the results of these spectra are summarized in Table 5. The C is presumed to be in the backbone of the structure because the intensity of the C-loss peak did not change with time under the electron beam.
• Typical XPS spectra of all films are compared in Figure 11. The peaks were fit and the results are summarized in Table 4. The Ti:0 ratios of the films are summarized in Table 7. The latter were obtained from the areas of the Ti peaks at ⁇ 459 eV peak and the O peaks at ⁇ 530 eV peak. Here the ratio is roughly 1:3.
• the BEs after ethanol washing, LiCl and even after TGA to 800 °C are all quite comparable indeed and thus the values obtained on these films can be considered representative of all BEs for all processing conditions.
• the films were heated in air the XPS spectra shifted (not shown).
• Fig. 13 shows that, except in the case of TriSiC2 for which a Si signal was observed (Fig. 13c), all other films were comprised of only three elements, Ti, O and C. There was also no Cl between the layers confirming that we are not dealing with double layered hydroxides (Fig. 13b).
• T1O2 is an outlier is because we have shown by XRD and TEM (Fig. 16) that what forms in this case is not a 2D structure, but rather nano-anatase particles. It is instructive at this point to compare the XRD diffraction patterns of anatase and our 2D flakes. In the latter the (104) and (105) peaks do not exist and the 63° 20 peak in anatase shifts much closer to 60° 20 (Fig. 16a).
• Figure 4b in main paper shows the galvanostatic charge/discharge voltage profiles at a specific current of 20 mA g 1 , the initial lithiation and delithiation specific capacities are 714 and 265 mAh g 1 , respectively.
• the specific capacity loss in the first lithiation process can be attributed to the solid electrolyte interphase (SEI) layer formation below 0.85 V and other irreversible reactions.
• SEI solid electrolyte interphase
• the specific capacity stabilizes after two cycles.
• the stable lithiation and delithiation specific capacities of 210 and 209 mAhg 1 , respectively, are maintained after 5 cycles.
• Figure 17a plots the electrochemical impedance spectroscopy of the electrode, showing low system resistance (4 W) and small charge transfer resistance (18 W), which support the electrochemical performance observed. Rate handling capability results are shown in Figure 17b.
• a reversible capacity of - 110 mAh g _1 can be maintained.
• a reversible capacity of - 80 mAh g 1 can be achieved, and by returning to 20 mA g 1 , the capacity recovered to -180 mAh g 1 .
• the as-prepared TCO electrode exhibits excellent cycling stability performance at a specific current of 100 mA g 1 .
• the electrode shows a specific capacity of 155 mAhg 1 over 200 cycles.
• the Coulombic efficiency of the electrode is - 98.9% after 30 cycles, reflecting a highly efficient electrochemical cycling.
• FIG 18a plots typical CV curves in the 1.8-2.6 V (vs. Li/Li + ) range at a scan rate of 0.1 mV s 1 .
• the CV curves show two sharp and distinct cathodic and one anodic peak.
• the first cathodic peak at 2.3 V is ascribed to S reduction (12) to long-chain lithium polysulfides (LiPs), while the second peak is related to a subsequent reduction of LiPs to Li26/Li2S.[17]
• the peak shifts after the first anodic peak are possibly due to nucleation/reorganization during the redeposition of the LiPs back to 12.
• Figure 4c displays typical discharge plateaus consistent with the CV results.
• the TCO/S composite electrodes deliver capacities of 1300, 1200, 1050 mAh g 1 at 0.1, 0.2 and 0.5 C rates, respectively. Such high capacity can be associated with the TiCO conductivity, coupled with possible surface-active sites that bind to the LiPs.
• Figure 14b shows the cell delivers an initial capacity of -1300 mAh g 1 , which stabilizes to -1000 mAh g 1 after the first 5 cycles. This initial drop is associated with the two conditioning cycles at low rate of 0.1 and 0.2 C.
• the composite delivers a capacity of -1000 mAh g 1 after ⁇ 300 cycles with around 100 % retention. The capacity drops after 300 cycles.
• XRD pattern of the powder showed low angle peak with d-spacing of 9.4 A, non-basal peaks at 25° and 48°, that correspond to 2D anatase. The (104) and (105) peaks were missing. Some low intensity peaks that belong to unreacted the TiB2 precursor remained.
• SEM micrographs (Fig. 19) of the resulting powder revealed an even distribution of well separated mesoporous particles roughly 10 pm in size.
• the mesoporous particles can be made of ligaments that are few-mi crons long and less than 100 nm in diameter.
• the mesoporous particles can be used in, e.g., drug delivery, energy storage, and devices.
• a therapeutic can be associated with the mesoporous particles (e.g., adsorbed to, intercalated into, etc.), which therapeutic-laden particles can be introduced to a subject and deliver the therapeutic to the subject.
• a composition comprising: a plurality of oxide-based nanofilaments and/or subnanofilaments, and optionally an amount of carbon.
• the nanofilaments can comprise titanium.
• the composition can be present as a mesoporous powder in which the powder particulates comprise the oxide- based nanofilaments and/or subnanofilaments.
• Aspect 2 The composition of Aspect 1, wherein at least some of the nanofilaments and/or subnanofilaments have a width in the range of from about 3 to about 50 A.
• the width can be, e.g., from about 3 to about 50 A, from about 5 to about 45 A, from about 7 to about 40 A, from about 9 to about 35 A, from about 12 to about 30 A, from about 15 to about 20 A, and all intermediate values and combinations.
• the composition can be comprised in a suspension, e.g., in a solution or an ink, which ink can be printable.
• inks can be sprayed, printed, or otherwise applied to a substrate.
• An ink can include solvents, binders, and the like.
• Aspect 3 The composition of Aspect 2, wherein at least some of the nanofilaments and/or subnanofilaments have an average width in the range of from about 7 to about 20 A.
• Aspect 4 The composition of any one of Aspects 1-3, wherein the nanofilaments and/or subnanofilaments define anon-circular cross-section.
• Aspect 5 The composition of Aspect 4, wherein the nanofilaments and/or subnanofilaments define a cross-sectional aspect ratio of from greater than 1 to about 10.
• the cross-sectional aspect ratio can be from 1.1 to 10, from 1.5 to 9, from 1.8 to 8, from 2.2 to 7, from 2.5 to 6, from 2.8 to 5, or even from 3.2 to 4.
• Aspect 6 The composition of Aspect 5, wherein the nanofilaments and/or subnanofilaments define a cross-sectional aspect ratio of from about 2 to about 5.
• Aspect 7 The composition of any one of Aspects 1-6, wherein the nanofilaments and/or subnanofilaments have an average cross-sectional area in the range of from about 10 to about 100 A 2 .
• the average cross-sectional area can be the range of from about 10 to about 100 A 2 , from about 15 to about 90 A 2 , from about 20 to about 80 A 2 , from about 30 to about 70 A 2 , from about 40 to about 60 A 2 , or even about 50 A 2 .
• Aspect 8 The composition of any one of Aspects 1-7, wherein at least some of the nanofilaments and/or subnanofilaments have a length in the range of from 1 nm to about 25 pm.
• the length can be, e.g., from about 1 nm to about 25 pm, from about 10 nm to about 20 pm, from about 50 nm to about 10 pm, from about 100 nm to about 5 pm, or from about 250 nm to about 2 pm.
• Aspect 9 The composition of Aspect 8, wherein at least some of the nanofilaments and/or subnanofilaments have a length in the range of from 1 nm to about 1 pm.
• Aspect 10 The composition of any one of Aspects 1-9, wherein the nanofilaments and/or subnanofilaments are comprised in a plurality of flakes; the nanofilaments and/or subnanofilaments can self-assemble into the flakes.
• the nanofilaments and/or subnanofilaments can be aligned in a plane; and a flake can include two or more layers of aligned nanofilaments and/or subnanofilaments, which can in turn provide a flake that is a well-ordered stack of nanofilament and/or subnanofilament layers.
• the nanofilaments can be self-aligning.
• Aspect 11 The composition of Aspect 7, wherein at least some of the plurality of flakes lie in a common plane.
• the flakes can be well-stacked along the stacking direction.
• the nanofilaments and/or subnanofilaments can result in in XRD patterns that are typical of 2D materials, i.e., only one family of planes diffract. Without being bound to any particular theory or embodiment, the nanofilaments and/or subnanofilaments can self-assemble into 2D flakes.
• Aspect 12 The composition of any one of Aspects 1-11, further comprising a pharmaceutically acceptable carrier.
• Aspect 13 The composition of any one of Aspects 1-12, further comprising one or more materials that are fatal to cancer cells.
• Aspect 14 The composition of any one of Aspects 1-13, further comprising a binder.
• a binder can be, e.g., a glue, an adhesive, or other matrix material.
• Aspect 15 The composition of Aspect 14, wherein the binder comprises a polymer.
• Aspect 16 The composition of any one of Aspects 1-15, wherein the nanofilaments and/or subnanofilaments exhibit a XRD pattern that, when compared to a XRD pattern of nano- or bulk anatase, exhibit reduced (104) and (105) peaks at around 38° and about 55° two theta (2Q).
• the disclosed nanofilaments and/or subnanofilaments can, in some embodiments, exhibit a Raman spectrum that is quite similar to that of bulk anatase, but can differ from bulk anatase in terms of the XRD spectrum, as described herein.
• Aspect 17 A device, the device comprising a composition according to any one of Aspects 1-16.
• Aspect 18 The device of Aspect 17, wherein the device comprises an electrode.
• Aspect 19 The device of Aspect 17, wherein the device is characterized as an energy storage device.
• a device can be, e.g., a battery, a supercapacitor, and the like.
• a device can be rechargeable, but can also be disposable.
• Such a device can be comprised in a mobile computing device, a mobile communications device, a computing device, an illumination device, a signal transmitted, a signal receiver,
• Aspect 20 The device of Aspect 18, wherein the electrode comprises a composition according to any one of Aspects 1-16.
• Aspect 21 The device of Aspect 17, wherein the device comprises a dispenser, the dispenser having disposed therein the composition according to any one of Aspects 1-16.
• a dispenser can be, e.g., a syringe, a nozzle, and the like.
• Such a dispenser can be used to deliver the composition (e.g., according to any one of Aspects 1-16) to a subject (e.g., a human patient) and/or to a sample obtained from a patient.
• a sample can be, e.g., a blood sample.
• Aspect 22 A method, comprising operating a device according to Aspect 17.
• a method comprising: contacting a mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal with a quaternary ammonium salt and/or base, the mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal optionally being non- water-soluble, the non-water soluble binary, or ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide optionally comprising a transition metal, the transition metal optionally comprising titanium, the contacting being performed under conditions sufficient to give rise to a nanofilamentous (and/or subnanofilamentous) product.
• the product can self-assemble into 2D flakes.
• Example carbides include, e.g., titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, tantalum carbide, chromium carbide, molybdenum carbide, tungsten carbide, iron carbide, and the like.
• Example nitrides include, e.g., aluminum nitride, boron nitride, calcium nitride, cerium nitride, europium nitride, gallium nitride, indium nitride, lanthanum nitride, lithium nitride, magnesium nitride, niobium nitride, silicon nitride, strontium nitride, tantalum nitride, titanium nitride, vanadium nitride, zinc nitride, zirconium nitride, and the like.
• Example borides include, e.g., aluminium diboride, aluminium dodecaboride, aluminium magnesium boride, barium boride, calcium hexaboride, cerium hexaboride, chromium(III) boride, cobalt boride, dinickel boride, erbium hexaboride, erbium tetraboride, hafnium diboride, iron boride, iron tetraboride, lanthanum hexaboride, magnesium diboride, nickel boride, niobium diboride, osmium boride, plutonium borides, rhenium diboride, ruthenium boride, samarium hexaboride, scandium dodecaboride, silicon boride, strontium hexaboride, tantalum boride, titanium diboride, trinickel boride, tungsten boride, uran
• Example phosphides include, e.g., alminium gallium indium phosphide, aluminium gallium phosphide, aluminium phosphide, bismuth phosphide, boron phosphide, cadmium phosphide, calcium monophosphide, calcium phosphide, carbon monophosphide, cobalt(II) phosphide, copper(I) phosphide, dysprosium phosphide, erbium phosphide, europium(III) phosphide, ferrophosphorus, gadolinium phosphide, gallium arsenide phosphide, gallium indium arsenide antimonide phosphide, gallium phosphide, holmium phosphide, indium arsenide antimonide phosphide, indium gallium arsenide phosphide, indium gallium phosphide,
• Example aluminides include, e.g., magnesium aluminide, titanium aluminide, iron aluminide, and nickel aluminide.
• Example silicides include, e.g., nickel silicide, sodium silicide, magnesium silicide, platinum silicide, titanium silicide, tungsten silicide, and molybdenum silicide.
• mono-, binary, or ternary, or higher carbides, nitrides, borides, phosphides, aluminides, or silicides that comprise titanium are particularly suitable.
• titanium sponge is considered a particularly suitable form of titanium metal for use with the disclosed technology. For example, one can contact titanium sponge with a quaternary ammonium salt as described herein so as to give rise to a nanofilamentous (or subnanofilamentous) product, as described herein.
• Aspect 24 The method of Aspect 23, wherein the conditions comprise a temperature of from 0 to 100 °C, to 200°C, or even to 300 °C for from about 0.5 hours to about 1, 2, 3, 4, or 5 weeks.
• the temperature can be constant during the time of exposure, but can also be varied, e.g., increased and/or decreased.
• the temperature can be, e.g., from about 0 to about 300 °C, from about 5 to about 95 °C, from about 10 to about 90 °C, from about 15 to about 85 °C, from about 20 to about 80 °C, from about 25 to about 75 °C, from about 30 to about 70 °C, from about 35 to about 65 °C, from about 40 to about 60 °C, from about 45 to about 55 °C, or even about 50 °C. Temperatures from 100 to 200 °C are also suitable. The temperature can be varied during the exposure (e.g., exposure to a first temperature and then a second temperature), but this is not a requirement.
• the exposure can be, e.g., according to a preprogrammed schedule that sets temperatures and/or durations of exposure.
• the exposure temperature can be, e.g., about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 90, about 95, or even about 100 °C.
• the conditions can, in some embodiments, comprise a temperature of from about 20 to about 300 °C and an exposure of from about 0.5 hours to about 2, 3, 4, or even 5 weeks.
• the conditions can comprise a temperature of about 100 to about 200 °C and an exposure of from about 1 hours to about 1 week.
• the temperature can be constant during the time of exposure, but can also be varied, e.g., increased and/or decreased.
• the temperature can be, e.g., from about 100 to about 200 °C, from about 105 to about 195 °C, from about 100 to about 190 °C, from about 115 to about 185 °C, from about 120 to about 180 °C, from about 25 to about 175 °C, from about 130 to about 170 °C, from about 135 to about 165 °C, from about 140 to about 160 °C, from about 145 to about 155 °C, or even about 150 °C.
• the temperature can be varied during the exposure (e.g., exposure to a first temperature and then a second temperature), but this is not a requirement.
• the exposure can be, e.g., according to a preprogrammed schedule that sets temperatures and/or durations of exposure.
• the exposure temperature can be, e.g., about 125, about 130, about 135, about 140, about 145, about 150, about 155, about 160, about 165, about 170, about 175, about 180, about 190, about 195.
• the method can be performed in a closed system, e.g., in a pressure vessel.
• the pressure can be atmospheric, but can also be less than atmospheric pressure or even can be greater than atmospheric pressure, e.g., a pressure of greater than 1 atmosphere (101.325 kPa) to about 10 atmospheres (1013.250 kPa).
• the period of exposure (which can be termed a “reaction time”) can be, e.g., from about 1 hours to about 7 days, from about 5 hours to about 6 days, from about 15 hours to about 5 days, from about 20 hours to about 4 days, from about 24 hours to about 3 days, or even about 2 days.
• the exposure can be for from 12 hours to about 72 hours, about 15 hours to about 70 hours, about 18 hours to about 64 hours, about 24 hours to about 60 hours, about 30 hours to about 55 hours, about 33 hours to about 52 hours, about 37 hours to about 48 hours, about 40 hours to about 45 hours, and all intermediate values and sub-combinations of ranges.
• Aspect 25 The method of Aspect 23, comprising contacting a mono-, binary, ternary, or higher boride (which can comprise Ti) with a quaternary ammonium salt and/or base so as to give rise to a product, which product can be nanofilamentous and/or subnanofilamentous.
• a mono-, binary, ternary, or higher boride which can comprise Ti
• a quaternary ammonium salt and/or base so as to give rise to a product, which product can be nanofilamentous and/or subnanofilamentous.
• Aspect 26 The method of Aspect 25, wherein the binary boride comprises one or more titanium borides.
• Aspect 27 The method of any one of Aspects 23-26, wherein the quaternary ammonium salt and/or base comprises an ammonium hydroxide, an ammonium halide, or any combination thereof.
• Aspect 28 The method of Aspect 27, wherein the quaternary ammonium hydroxide comprises tetramethyl ammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide (TPAOH), tetrabutylammonium hydroxide (TBAOH), ammonium hydroxide (NTUOH), their amine derivatives, or any combination thereof.
• TMAOH tetramethyl ammonium hydroxide
• TEAOH tetraethylammonium hydroxide
• TPAOH tetrapropylammonium hydroxide
• TAAOH tetrabutylammonium hydroxide
• NTUOH ammonium hydroxide
• Aspect 29 The method of Aspect 27, wherein the quaternary ammonium salt comprises a quaternary ammonium chloride, a quaternary ammonium bromide, a quaternary ammonium iodide, a quaternary ammonium fluoride, or any combination thereof. It should be understood that one can use either or both of a quaternary ammonium salt and a quaternary ammonium base.
• Aspect 30 The method of any one of Aspects 23-29, further comprising filtering the product.
• Aspect 31 The method of any one of Aspects 23-30, further comprising washing the product with a metal salt and/or other water-soluble metal compound.
• the metal salt can be a metal halide salt, e.g., a Li halide, a Na halide, a K halide, an Rb halide, a Cs halide, a Fr halide, a Be halide, a Mg halide, a Ca halide, a Sr halide, a Ba halide, a Ra halide, a Mn halide, a Fe halide, a Ni halide, a Co halide, a Cu halide, a Zn halide, a Mo halide, aNb halide, a W halide, or any combination thereof.
• a metal halide salt e.g., a Li halide, a Na halide, a K halide, an Rb halide, a Cs halide, a Fr halide, a Be halide, a Mg halide, a Ca
• Aspect 32 The method of any one of Aspects 23-31, further comprising washing the product with a metal salt and/or water-soluble metal compounds.
• the metal salt can optionally comprise metal sulfate, nitrate, chromate, acetate, carbonate, permanganate, or metal hydroxide, or any combination of thereof.
• Aspect 33 The method of Aspect 32, wherein the metal in the salt can be essentially any metal from the periodic table.
• the metal in the metal salt can be Li, Na, K, Cs, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Cd, Ta, or W, or any combination of thereof.
• a metal salt can be, e.g., LiCl, KC1, NaCl, LiF, KF, NaF, LiOH, KOH, NaOH, or any combination thereof.
• Aspect 34 The method of any one of Aspects 32-33, wherein the metal salt is LiCl, KC1, NaCl, LiF, CsCl, KF, NaF, LiOH, KOH, NaOH, or any combination thereof.
• Aspect 35 The method of any one of Aspects 32-33, wherein the metal salt comprises CrCb, MnCh, FeCh, FeCb, CoCh, NiCh, MoCb, FeS04, (NH4)2Fe(S04)2, CuCh, CuCl, ZnCh or any combination thereof.
• Aspect 36 The method of any one of Aspects 23-35, wherein the product is a composition according to any one of Aspects 1-16.
• Aspect 37 The method of any one of Aspects 23-36, wherein the nanofilamentous (and/or subnanofilamentous) product exhibits a XRD pattern that, when compared to a XRD pattern of nano- or bulk anatase, exhibit reduced (104) and (105) peaks at around 38° and about 55° two theta (2Q).
• the disclosed nanofilaments and/or subnanofilaments can, in some embodiments, exhibit a Raman spectrum that is similar to that of bulk anatase, but can differ from bulk anatase in terms of the XRD spectrum, as described herein.
• a method comprising:
• the nanoparticulate product optionally at least some nanoparticles having a diameter of from about 2 nm to about 1000 nm, optionally from about 10 to about 100 nm.
• the nanoparticulate product can be further processed, e.g., by heating, by further reaction, and the like.
• the further processing can be performed to coarsen the product, e.g., to give rise to larger-size particles, e.g., from about 0.1 to about 0.7 pm, or from about 0.2 to about 0.5 pm.
• the disclosed methods for making an anatase product of the present disclosure provide a substitute for TiCh (including pigment-grade TiCh) and also provide an improvement over existing processes for making such TiCh, in particular pigment- grade TiCh.
• the contacting can be at from about 20 to about 80 °C, or from about 25 to about 75 °C, or from about 30 to about 70 °C, or from about 35 to about 65 °C, or from about 40 to about 60 °C, or from about 45 to about 55 °C, even about 50 °C.
• the contacting can be from , e.g., about 5 minutes to about 5 hours, from about 10 minutes to about 4.5 hours, from about 15 minutes to about 4 hours, from about 20 minutes to about 3.5 hours, from about 30 minutes to about 3 hours, from about 45 minutes to about 2 hours, or any combination or subrange thereof.
• Aspect 39 The method of Aspect 38, wherein the quaternary ammonium salt and/or base comprises an ammonium hydroxide, an ammonium halide, or any combination thereof.
• Aspect 40 The method of Aspect 38, wherein the quaternary ammonium base comprises tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), tetrapropylammonium hydroxide (TPAOH), tetrabutylammonium hydroxide (TBAOH), ammonium hydroxide (NH4OH), their amine derivatives, or any combination thereof.
• TMAOH tetramethylammonium hydroxide
• TEAOH tetraethylammonium hydroxide
• TPAOH tetrapropylammonium hydroxide
• TSAOH tetrabutylammonium hydroxide
• NH4OH ammonium hydroxide
• Aspect 41 The method of Aspect 38, wherein the quaternary ammonium salt comprises a quaternary ammonium chloride, a quaternary ammonium bromide, a quaternary ammonium iodide, a quaternary ammonium fluoride, or any combination thereof. As described elsewhere herein, one can use either or both of a quaternary ammonium salt and a quaternary ammonium base.
• Aspect 42 The method of any one of Aspects 38-41, further comprising filtering the product.
• a composition comprising a population of anatase nanoparticles made according to any one of Aspects 38-42.
• Such nanoparticles can be in the size range of from about 200 nm to about 600 nm, e.g., from about 200 nm to about 600 nm, from about 225 to about 575 nm, from about 250 to about 550 nm, from about 275 nm to about 525 nm, from about 300 to about 500 nm, from about 325 to about 475 nm, from about 350 to about 450 nm, from about 375 to about 425 nm, or even about 400 nm.
• Aspect 44 A method, comprising replacing T1O2 with a population of anatase nanoparticles made according to any one of Aspects 38-42.
• a pigment normally made with traditional T1O2 by replacing the traditional T1O2 with anatase nanoparticles according to the present disclosure, e.g., according to any one of Aspects 38-42.
• a method comprising: contacting a mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal with a quaternary ammonium salt and/or base, the mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal optionally being non- water-soluble, the non-water soluble binary, or ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide optionally comprising a transition metal, the transition metal optionally comprising titanium, the contacting optionally performed while shaking, and the contacting being performed under conditions sufficient to give rise to mesoporous particles.
• a method comprising: contacting a mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal with a quaternary ammonium salt and/or base, the mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal optionally being non- water-soluble, the non-water soluble binary, or ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide optionally comprising a transition metal, the transition metal optionally comprising titanium, the contacting optionally performed while shaking, the contacting being followed by washing with at least one salt and performed under conditions sufficient to give rise to mesoporous particles.
• a method comprising: contacting a mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal with a quaternary ammonium salt and/or base, the mono-, binary, ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide, or titanium metal optionally being non- water-soluble, the non-water soluble binary, or ternary, or higher carbide, nitride, boride, phosphide, aluminide, or silicide optionally comprising a transition metal, the transition metal optionally comprising titanium, the contacting performed while shaking and at a temperature of from about 50 to about 95 °C, followed by washing with LiCl to give rise to mesoporous particles.
• Aspect 48 A composition comprising mesoporous particles made according to any one of claims 45-47.
• the mesoporous particles can exhibit a XRD pattern that, when compared to a XRD pattern of nano- or bulk anatase, exhibit reduced (104) and (105) peaks at around 38° and about 55° two theta (2Q).
• the disclosed mesoporous particles can, in some embodiments, exhibit a Raman spectrum that is quite similar to that of bulk anatase, but can also differ from bulk anatase in terms of the XRD spectrum, as described herein. [00281] Aspect 49.
• a composition comprising mesoporous particles, wherein the mesoporous particles comprise titanium and wherein the mesoporous particles exhibit a XRD pattern that, when compared to a XRD pattern of nano- or bulk anatase, exhibit reduced (104) and (105) peaks at around 38° and about 55° two theta (2Q).
• the disclosed mesoporous particles can, in some embodiments, exhibit a Raman spectrum that is quite similar to that of bulk anatase, but can also differ from bulk anatase in terms of the XRD spectrum, as described herein.
• Aspect 50 The composition according to any one of claims 48-49, further comprising a therapeutic.
• a method comprising effecting delivery of a therapeutic to a subject, the therapeutic being comprised in a composition according to any one of claims 48-49.
• Aspect 52 An electrode, the electrode comprising a composition according to any one of claims 48-49.
• a device comprising a composition according to any one of claims 48-49.
• Aspect 54 The device of claim 52, wherein the device is an energy storage device.
• Aspect 55 A method, the method comprising operating the device of any one of claims 52-53.

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• 2022
  • 2022-02-11 WO PCT/US2022/070644 patent/WO2022174264A1/en not_active Ceased
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