MULTIDIMENSIONAL MULTILAYERED UPCONVERSION NANOARCHITECTONICS WITH TUNEABLE ND CONTENT FOR EFFICIENT PHOTOCATALYTIC PHENOLIC DEGRADATION UNDER AMBIENT CONDITIONS

Abstract

Provided herein are multilayered, multidimensional upconversion nanomaterial compositions and methods. In certain aspects and embodiments, the compositions and methods are useful in the photolytic degradation of a phenolic pollutant (e.g., phenol).

Claims

1. A multi-layered upconversion nanoparticle comprising: an active core, wherein the active core comprises Er; an intermediate layer, wherein the intermediate layer comprises Yb; and an exterior layer; wherein the intermediate layer is between the active core and the exterior layer, and wherein the exterior layer comprises Nd.

2. The multi-layered upconversion nanoparticle of claim 1, wherein the active core is spherical or semispherical.

3. The multi-layered upconversion nanoparticle of claim 1, wherein the active core comprises NaYF.sub.4:Yb,Er,Ca.

4. The multi-layered upconversion nanoparticle of claim 1, wherein the intermediate layer is hexagonal or octagonal.

5. The multi-layered upconversion nanoparticle of claim 1, wherein the intermediate layer comprises NaYF.sub.4:Yb,Ca.

6. The multi-layered upconversion nanoparticle of claim 1, wherein the outer layer is sandglass-like or star-like.

7. The multi-layered upconversion nanoparticle of claim 1, wherein the outer layer comprises NaNdF.sub.4:Yb.

8. The multi-layered upconversion nanoparticle of claim 1, wherein the outer layer comprises from about 10% to 80% w/w Nd.

9. The multi-layered upconversion nanoparticle of claim 8, wherein the outer layer comprises at least 20% w/w Nd.

10. The multi-layered upconversion nanoparticle of claim 9, wherein the outer layer comprises at least 40% w/w Nd.

11. The multi-layered upconversion nanoparticle of claim 10, wherein the outer layer comprises at least 60% w/w Nd.

12. The multi-layered upconversion nanoparticle of claim 1, wherein the active core is spherical; wherein the intermediate layer is hexagonal; and wherein the outer layer is sandglass-like.

13. The multi-layered upconversion nanoparticle of claim 1, wherein the active core is semispherical; wherein the intermediate layer is octagonal; and wherein the outer layer is star-like.

14. A method for degrading a phenolic pollutant in a medium, the method comprising exposing a mixture of the medium and the multi-layered upconversion nanoparticle of claim 1 to light.

15. The method of claim 14, wherein the phenolic pollutant is phenol.

16. The method of claim 14, wherein the phenolic pollutant is a dye.

17. The method of claim 14, wherein the medium is wastewater.

18. The method of claim 14, wherein the light is visible light.

19. The method of claim 14, wherein the light is near infrared light (NIR).

20. A method for preparing the multi-layered upconversion nanoparticle of claim 1, the method comprising using an active core particle as a seed for growth of the intermediate layer to produce a core-shell particle; and using the core-shell particle as a seed for growth of the outer layer to produce the multi-layered upconversion nanoparticle.

21. The method of claim 20, wherein the method is a seed-mediated growth method coupled with a solvothermal method.

22. The method of claim 20, wherein the intermediate layer is hexagonal or octagonal.

23. The method of claim 20, wherein the outer layer is sandglass-like.

24. The method of claim 20, wherein the outer layer is star-like.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0017] FIGS. 1A-1C show the composition of multidirectional, multilayered NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4:Yb,Ca@NaNdF.sub.4:Yb sandglass-like nanoarchitectonics, with (a) a 3D model of an exemplary sandglass-like structure, (b) a transmission electron microscopy (TEM) image, and (c) inductively coupled plasma-optical emission spectrometry (ICP-OES) results.

[0018] FIGS. 2A-2C show the composition of multidirectional, multilayered NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4:Yb,Ca@NaNdF.sub.4:Yb star-like nanoarchitectonics, with (a) a 3D model of an exemplary star-like structure, (b) a TEM image, and (c) ICP-OES results.

[0019] FIGS. 3A-3C show the composition of core-shell hexagonal NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4:Yb nanoarchitectonics, with (a) a 3D model of an exemplary core-shell hexagonal structure, (b) a TEM image, and (c) ICP-OES results.

[0020] FIGS. 4A-4C show the composition of semispherical NaYF.sub.4:Yb,Er,Ca nanoarchitectonics, with (a) a 3D model of an exemplary semispherical structure, (b) a TEM image, and (c) ICP-OES results.

[0021] FIGS. 5A-5D show additional experimental data for the as-synthesized sandglass-like nanoarchitectonics, with (a) an X-ray diffraction (XRD) spectrum of the sandglass-like structure, (b) X-ray photoelectron spectroscopy (XPS) survey results, (c) upconversion luminescence (UCL) results under 808 nm excitation with a power density of 1.5 W cm.sup.−2, and (d) ultraviolet (UV) absorbance of the as-synthesized sandglass-like nanoarchitectonics.

[0022] FIGS. 6A-6C show additional experimental data for the as-synthesized star-like nanoarchitectonics, with (a) an XRD spectrum of the exemplary star-like structure, (b) XPS survey results, and (c) UCL results under 808 nm excitation with a power density of 1.5 W cm.sup.−2.

[0023] FIGS. 7A-7C show additional experimental data for core-shell hexagonal nanoarchitectonics, with (a) an XRD spectrum of the core-shell hexagonal structure, (b) XPS survey results, and (c) UCL results under 808 nm excitation with a power density of 1.5 W cm.sup.−2.

[0024] FIGS. 8A-8C show additional experimental data for semispherical nanoarchitectonics, with (a) an XRD spectrum of the semispherical structure, (b) XPS survey results, and (c) UCL results under 808 nm excitation with a power density of 1.5 W cm.sup.−2.

[0025] FIGS. 9A-9B show the results of photocatalytic phenol degradation on multilayered, multidimensional NaYF.sub.4: Yb,Er,Ca@NaYF.sub.4: Yb,Ca@NaNdF.sub.4:Yb, sandglass-like (90% Nd) nanoarchitectonics (a) with H.sub.2O.sub.2 and (b) without H.sub.2O.sub.2.

[0026] FIGS. 10A-10B show the results of photocatalytic phenol degradation on multilayered, multidimensional NaYF.sub.4: Yb,Er, C a@NaYF.sub.4: Yb, C a@NaNdF.sub.4:Yb, sandglass-like (80% Nd) nanoarchitectonics (a) without H.sub.2O.sub.2 and (b) with H.sub.2O.sub.2.

[0027] FIGS. 11A-11B show the results of photocatalytic phenol degradation on multilayered, multidimensional NaYF.sub.4: Yb,Er,Ca@NaYF.sub.4: Yb,Ca@NaNdF.sub.4:Yb, sandglass-like (60% Nd) nanoarchitectonics (a) without H.sub.2O.sub.2 and (b) with H.sub.2O.sub.2.

[0028] FIGS. 12A-12B show the results of photocatalytic phenol degradation on multilayered, multidimensional NaYF.sub.4: Yb,Er,Ca@NaYF.sub.4: Yb,Ca@NaNdF.sub.4:Yb, sandglass-like (40% Nd) nanoarchitectonics (a) without H.sub.2O.sub.2 and (b) with H.sub.2O.sub.2.

[0029] FIGS. 13A-13B show the results of photocatalytic phenol degradation on multilayered, multidimensional NaYF.sub.4: Yb,Er, C a@NaYF.sub.4: Yb, C a@NaNdF.sub.4:Yb, spatical star-like (80% Nd) nanoarchitectonics (a) without H.sub.2O.sub.2 and (b) with H.sub.2O.sub.2.

[0030] FIGS. 14A-14B show the results of photocatalytic phenol degradation on multilayered, multidimensional NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4:Yb,Ca core-shell hexagonal nanostructure (a) with H.sub.2O.sub.2 and (b) without H.sub.2O.sub.2.

[0031] FIGS. 15A-15B show the results of photocatalytic phenol degradation on multilayered, multidimensional NaYF.sub.4: Yb,Er,Ca@NaYF.sub.4:Yb,Ca core-shell octagonal nanostructure (a) without H.sub.2O.sub.2 and (b) with H.sub.2O.sub.2.

[0032] FIGS. 16A-16B show the results of photocatalytic phenol degradation on NaYF.sub.4:Yb,Er,Ca semispherical core photocatalyst (a) without H.sub.2O.sub.2 and (b) with H.sub.2O.sub.2.

[0033] FIG. 17 shows photocatalytic phenol degradation on commercial TiO.sub.2 nanoparticle photocatalyst with and without H.sub.2O.sub.2.

[0034] Illustrative embodiments of the present invention are described in detail below with reference to the attached drawing figures, which are incorporated by reference herein.

DETAILED DESCRIPTION

[0035] Provided herein are compositions and methods directed to the rational fabrication of wide ranges of multi- and multidimensional upconversion nanoarchitectonics with controllable shapes and compositions based on epitaxial growth.

[0036] The as-synthesized upconversion nanoarchictonics possess various unique physicochemical merits including, massive active sites, strong energy absorption, effective energy transfer, intense nonblinking upconversion luminescence, and without energy back transfer or quenching, which are highly required for various catalytic applications. The fabrication approach is facile, one-step, template-free, productive, and versatile for the preparation of freestanding or supported upconversion nanoarchitectonics. The obtained multilayered nanoarchictonics involve multiple sanitizers with tunable contents and multidimensional, anisotropic, and outstanding surface merits (e.g., branches, cavities, or corners) that provide massive adsorption sites for the light absorption. The newly designed upconversion nanoarchitectonics allowed the efficient photocatalytic degradation of phenol (e.g., within only 35 min at room temperature).

Definitions

[0037] When referring to the compounds, composites, compositions, and methods provided herein, the following terms and phrases have the following meanings unless indicated otherwise. Unless defined otherwise, all technical and scientific terms and phrases used herein have the same meaning as is commonly understood by one of ordinary skill in the art. If there is a plurality of definitions for a term or phrase provided herein, these Definitions prevail unless stated otherwise.

[0038] As used herein, “a,” “an,” or “the” can include not only includes aspects and embodiments with one member, but also aspects and embodiments with more than one member. For example, an aspect comprising “a component selected from the group consisting of X, Y, and Z” may present embodiments comprising X, Y, Z, X in combination with Y, Y in combination with Z, X in combination with Z, or all three (X, Y, and Z) in combination.

[0039] As used herein, “nanoscale” refers to particles having a size of less than 100 nm.

[0040] As used herein, “independently” refers to the relationship among multiple instances of the same variable when selected from the same set of possibilities (e.g., a Markush group). For example, if the variable X is selected independently from the group consisting of a, b, and c, each instance of X in a structure can be the same as (e.g., all “a”) or be different from any other instance of X (e.g., for three “X,” one “b” and two “a” or any other combination of a, b, and c).

[0041] Typically, for at least some embodiments of a group as disclosed herein (e.g., “A, B, or C”; “the member selected from the group consisting of A, B, and C”), members of the group are (1) independently selected from the alternatives and (2) groups do not exclude the possibility of embodiments comprising combinations of the individual group members.

[0042] As used herein, “or” is not exclusive (i.e., “or” may be equivalent to “and/or”). For example, an aspect comprising “A, B, or C” may present embodiments with A, B, C, A in combination with B, B in combination with C, A in combination with C, or all three (A, B, and C) in combination.

[0043] As used herein, “zero-dimensional” nanomaterials (e.g., nanoparticles) refer to nanomaterials where all the dimensions of the nanomaterials are measured within the nanoscale. For example, in certain embodiments, no dimension of the nanomaterial is larger than 100 nm. In certain embodiments, zero-dimensional nanomaterials are nanoparticles.

[0044] As used herein, “one-dimensional” nanomaterials (e.g., nanosheets) refer to nanomaterials where at least one dimension is outside of the nanoscale. For example, in certain embodiments, when one dimension of the nanomaterial is larger than 100 nm. In certain embodiments, one-dimensional nanomaterials are nanosheets.

[0045] As used herein, “two-dimensional” nanomaterials (e.g., nanosheets) refer to nanomaterials where at least two dimensions are outside the nanoscale. For example, in certain embodiments, two dimensions of the nanomaterial are larger than 100 nm. In certain embodiments, two-dimensional nanomaterials are plate-like shapes. In certain embodiments, two-dimensional nanomaterials include, without limitation, nanofilms, nanolayers, and nanocoatings.

[0046] As used herein, “three-dimensional” materials refer to materials where each dimension is outside the nanoscale.

[0047] As used herein, “multidimensional” materials refer to materials where different layers or domains may have different dimensions. For example, a multilayered multidimensional material of the instant invention include a zero-dimensional core and a one- or two-dimensional outer layer.

[0048] As used herein, “w/w” refers to a percentage by weight. Unless specified otherwise, percentages disclosed herein are percentage by weight—that is, [(weight of a component)/(total weight of all components)]×100.

Compositions

[0049] In certain embodiments, this invention is directed to the rational design of novel kind of upconversion nanoarchitectonics materials with tunable Nd content.

[0050] This invention also reports a new use for upconversion as photocatalysis along with a substantial improvement of the photocatalytic properties of commercial TiO.sub.2 catalyst.

[0051] The obtained upconversion nanoarchitectonics were utilized for photocatalytic phenol degradation within a few minutes under ambient conditions. The invention includes the fabrication of multilayered multidimensional upconversion star-like composed of an active interior (NaYF.sub.4:Yb,Er,Ca) in a spherical shape, second layer (NaYF.sub.4:Yb,Ca) in a hexagonal shape and exterior layer (NaNdF.sub.4:Yb,Ca) in spatial dendritic shape with Nd of (80% w/w).

[0052] The invention comprises the synthesis of multilayered, multidimensional upconversion sandglass nanoarchitectonics composed of an active interior (NaYF.sub.4:Yb,Er,Ca) in a semispherical shape, an intermediate layer (NaYF.sub.4:Yb,Ca) in hexagonal shape, and an outer layer (NaNdF.sub.4:Yb,Ca) in sandglass shape with Nd of (10-80% w/w).

[0053] The fabrication process is based on seed-mediated, and the epitaxial growth is under solvothermal conditions. The synthetic method is facile, one-step, template-free, and versatile for the synthesis of upconversion nanoarchitectonics with controllable shapes and composition in a high yield with high feasibility for large-scale applications. Mainly, initial core nanoparticles is prepared by the solvothermal approach that is subsequently used as seeds for supporting the epitaxial growth of the second layer to form core-shell nanostructure. That is also used as seeds for the epitaxial growth of the third layer to form core@multiple shell nanoarchitectonics.

[0054] The method allows the high-mass production of freestanding or supported nanoarchitectonics with different morphologies and compositions.

[0055] The obtained upconversion nanoarchitectonics comprise the unique physiochemical properties of multidimensional shape (i.e., high surface area to volume ratio, massive active sites, non-autofluorescence, high chemical stability, large light-penetration depth, long lifetime, and strong energy absorption with inferior energy back transfer). This is in addition to impressive properties of multilayered shape (i.e., effective energy transfer, strong, nonblinking upconversion luminescence (UCL), long-distance between the inner cores and exterior shell from the shell, quick energy migration, and without cross-relaxation and quenching).

[0056] The Nd.sup.3+ in the outer shell act as a sensitizer and enhance the NIR photons absorption. Meanwhile, Yb.sup.3+ in the intermediate layer act as a bridge for energy transfer from Nd.sup.3+ to Er.sup.3+ activator in the inner core besides avoiding energy back-transfer and quenching from Er.sup.3+ and Nd.sup.3+, respectively.

[0057] The as-developed upconversion nanoarchitectonics allowed the significant enhancement in the photocatalytic phenol degradation with less than 35 min that is highly beneficent compared to traditional photocatalysts that need several hours.

[0058] In certain aspects and embodiments, provided herein is a multi-layered upconversion nanoparticle including: [0059] an active core, wherein the active core includes Er (e.g., Er.sup.3+); [0060] an intermediate layer, wherein the intermediate layer includes Yb (e.g., Yb.sup.3+); and [0061] an exterior layer; wherein the intermediate layer is between the active core and the exterior layer, and wherein the exterior layer includes Nd (e.g., Nd.sup.3+).

[0062] In certain embodiments, the active core is spherical or semispherical. In certain embodiments, the active core is spherical. In certain embodiments, the active core is semispherical.

[0063] In certain embodiments, the active core includes NaYF.sub.4:Yb,Er,Ca. In certain embodiments, the active core is NaYF.sub.4:Yb,Er,Ca.

[0064] In certain embodiments, the intermediate layer is hexagonal or octagonal. In certain embodimetns, the intermediate layer is hexagonal. In certain embodiments, the intermediate layer is octagonal.

[0065] In certain embodiments, the intermediate layer includes NaYF.sub.4:Yb,Ca. In certain embodiments, the intermediate layer is NaYF.sub.4:Yb,Ca.

[0066] In certain embodiments, the outer layer is sandglass-like or star-like. In certain embodimetns, the outer layer is sandglass-like. In certain embodiments, the outer layer is star-like.

[0067] In certain embodiments, the outer layer includes NaNdF.sub.4:Yb. In certain embodiments, the outer layer is NaNdF.sub.4:Yb.

[0068] In certain embodiments, the outer layer includes from about 10% to 80% w/w Nd (e.g. about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80%). In certain embodiments, the outer layer includes at least about 20% w/w Nd (e.g., at least about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, or 39%). In certain embodiments, the outer layer includes at least about 30% w/w Nd. In certain embodiments, the outer layer includes at least about 40% w/w Nd (e.g., at least about 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, or 59%). In certain embodiments, the outer layer includes at least about 50% w/w Nd. In certain embodiments, the outer layer includes at least about 60% w/w Nd (e.g., at least about 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, or 79%). In certain embodiments, the outer layer includes at least about 70% w/w Nd.

[0069] In certain aspects and embodiments, the active core is spherical; the intermediate layer is hexagonal; and the outer layer is sandglass-like. In certain aspects and embodiments, the active core is semispherical; the intermediate layer is octagonal; and the outer layer is star-like.

[0070] In certain aspects and embodiments, provided herein are compositions including hexagonal core-shells nanoparticles. In certain embodiments, the nanoparticles include NaYF.sub.4: Yb, Er, Ca@NaYF.sub.4: Yb, Ca UCNPs core-shells nanoparticles.

[0071] In certain embodiments, the compositions include multidimensional multilayered star-like nanoarchitectonics. In certain embodiments, the composition include multidimensional multilayered sandglass nanoarchitectonics.

[0072] Further disclosure is provided containing all the technical descriptions of the invention, including the obtained preparation, characterization, and results.

Methods for Preparing Upconversion

[0073] In certain aspects and embodiments, provided herein are methods for preparing the multi-layered upconversion composition as otherwise presented herein (e.g., a seed-mediated growth method coupled with a solvothermal method), the method including [0074] using an active core particle as a seed for growth of the intermediate layer to produce a core-shell particle; and [0075] using the core-shell particle as a seed for growth of the outer layer to produce the multi-layered upconversion nanoparticle.

[0076] In certain embodiments, provided herein are methods of preparing hexagonal core-shell nanoparticles, including: [0077] synthesizing hexagonal core-shell nanoparticles as otherwise disclosed herein.

[0078] In certain embodiments, provided herein are methods of preparing multidimensional multilayered nanoparticles, including: [0079] synthesizing multidimensional multilayered nanoparticles from hexagonal core-shell nanoparticles as otherwise disclosed herein.

[0080] In certain embodiments, the intermediate layer is hexagonal or octagonal. In certain embodiments, the intermediate layer is hexagonal. In certain embodiments, the intermediate layer is octagonal.

[0081] In certain embodiments, the outer layer is sandglass-like or star-like In certain embodiments, the intermediate layer is sandglass-like. In certain embodiments, the intermediate layer is star-like.

Methods of Degrading a Phenolic Pollutant

[0082] In certain aspects, provided herein are methods of treating a medium (e.g., water) comprising a phenolic pollutant (e.g., phenol) using any of the compositions described herein. Certain embodiments of any of the composites described elsewhere herein are contemplated to provide for treating water.

[0083] In certain aspects, provided herein is a method for degrading a phenolic pollutant (e.g., phenol) in a medium, the method including [0084] exposing a mixture of the medium and the multi-layered upconversion nanoparticle as otherwise taught herein to light.

[0085] In certain embodiments, the light is visible light. In certain embodiments, the light is near infrared light (NIR).

[0086] In certain aspects and embodiments, provided herein is a method of photolytically degrading a phenolic pollutant (e.g., phenol), including:

[0087] treating a phenolic pollutant (e.g., phenol) with light in the presence of a composition as otherwise disclosed herein (e.g., a sandglass-like or a star-like upconversion nanoparticle).

[0088] In certain embodiments, the method further includes exposing the mixture to near-infrared radiation.

[0089] In certain embodiments, the degradation is >70% complete (e.g., at least 70, 75, 80, or 90%). In certain embodiments, the degradation is >90% complete (e.g., at least 90, 93, 95, 97, 98, or 99%).

[0090] In certain embodiments, the use of a composition as otherwise taught herein enhanced the photocatalytic performance of phenolic pollutant (e.g., phenol) degradation in water at room temperature under visible light by more than 2 times compared to TiO.sub.2 alone in the presence and in the absence of H.sub.2O.sub.2.

[0091] In certain embodiments, the methods are directed to treating and purifying a medium using any of the aspects and embodiments of compositions described herein. Certain embodiments of any of the compositions described elsewhere herein are contemplated to provide for the removal, or an improved removal, of phenolic pollutants from the treated medium (i.e., one or more phases or mixtures of phases, such as a contaminated liquid or gas, the phase or phases comprising one or more impurity compounds or pollutants).

[0092] In certain embodiments, the phenolic pollutants are selected from the group consisting of phenol, p-chlorophenol, and p-nitrophenol. In certain embodiments, the phenolic pollutant is phenol. In certain embodiments, the phenolic pollutant isp-chlorophenol. In certain embodiments, the phenolic pollutant is p-nitrophenol.

[0093] In certain embodiments, the phenolic pollutant is a dye. In certain embodiments, a dye is an colored, aromatic compound that absorbs some wavelengths of light (e.g., quinone-imine dyes).

[0094] In certain embodiments, the medium is selected from the group consisting of water (e.g., wastewater), an oil medium, or a gaseous medium. In certain embodiments, the medium is wastewater. In certain embodiments, the wastewater comprises industrial wastewater or domestic wastewater. In certain embodiments, the phenolic pollutants are in water (e.g., process water or produced water comprising phenolic pollutants). In certain embodiments, the medium is an oil or a liquid comprising an oil. In certain embodiments, the medium is gaseous.

[0095] As would be appreciated by a person of skill in the art, phenol pollutants can be dissolved in wastewater. Pollutants can also be dissolved in oil(s). Moreover, phenol pollutants can be within a gaseous medium, for example, as volatilized pollutant species. In each of the medium described herein, the composites described herein can be used to remove phenol pollutants from one or more of each medium. In certain embodiments, the wastewater includes industrial wastewater. In certain embodiments, the wastewater includes domestic wastewater.

[0096] In certain embodiments, the inventive composition is used on an industrial scale. In certain embodiments, the inventive composition is used on domestic scale (i.e., a smaller scale that is more appropriate for use in a house or multi-family residence, such as an apartment).

[0097] In certain embodiments, the degrading pollutants in the medium (e.g., wastewater) occurs at room temperature.

[0098] In certain embodiments, the degrading pollutants in the medium (e.g., wastewater) occurs at atmospheric pressure.

[0099] In certain embodiments, the method removes the phenolic pollutants in less than 120 minutes (e.g., 120, 110, 100, 90, 80, 70, 60, 50, 40, or 30 min). In certain embodiments, the adsorbing pollutants from the wastewater removes the phenolic pollutants in less than 40 minutes (e.g., 40, 35, 30, or 25 min).

Examples

[0100] Provided herein are exemplary multilayered multidimensional nanoparticular compositions and methods for photolytic degradation of phenolic pollutants (e.g., phenol). Also provided herein are exemplary methods of preparing the compositions described herein.

[0101] Certain embodiments of the invention are illustrated by the following non—limiting examples. As used herein, the symbols and conventions used in these processes, schemes, and examples, regardless of whether a particular abbreviation is specifically defined, are consistent with those used in the contemporary scientific literature, e.g., the Journal of the American Chemical Society or Applied Surface Science. Specifically, but without limitation, the following abbreviations may be used in the Examples, and throughout the specification:

TABLE-US-00001 Abbreviation Term or Phrase Aq. aqueous ESI electrospray ionization hr, h, or hrs hours LC liquid chromatography MS mass spectrometry MW molecular weight ppm parts per million rt room temperature UV ultraviolet

Analysis Methods

[0102] The transmission electron microscope (TEM) images were recorded using (TEM, TecnaiG220, FEI, Hillsboro, OR, USA), equipped with an energy dispersive spectrometer (EDS), High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and high-resolution TEM (HRTEM). The X-ray photoelectron spectroscopy (XPS) was analyzed on a VGESCALAB MKII (VG XPS Scientific Ltd., UK) equipped with a monochromatic Al Kα radiation source (1486.6 eV) under a UHV environment (ca. 5×10.sup.−9 Torr). The X-ray diffraction pattern (XRD) was recorded on an X-ray diffractometer (D8 ADVANCE diffractometer (Broker Co., Germany). The upconversion luminescence (UCL) spectra were measured with an 808 nm laser from an optical parametric oscillator (OPO) (Continuum Sunlite) as the excitation source. The elemental analysis was performed by an ICAP 6000 ICP-OES system (Thermo Scientific, Waltham, MA, USA).

Example 1: Synthesis of Semispherical Upconversion Nanoparticle Core

[0103] All chemicals were used as received without any modifications. Semispherical upconversion NaYF.sub.4:Yb,Er,Ca nanoparticles were prepared by mixing YCl.sub.3, YbCl.sub.3, Ca(CH.sub.3COOH).sub.2, and ErCl.sub.3 with final concertation of 0.5 mol L.sup.−1 in oleic acid (10 mL) and 1-octadecene (10 mL) under stirring under N.sub.2, while heating at 150° C., then cooled down to 50° C. before the addition of CH.sub.3OH (5 mL) involving NH.sub.4F (1 mmol) and NaOH (1 mmol) for 20 min, then the solution was degassed while heating at 150° C. The mixture was heated to 300° C. under N.sub.2 and kept for 2 h 90 min before being cooled to room temperature followed by centrifugation at 10000 rpm and washing by ethanol for 3 times.

Example 2: Synthesis of Semispherical Upconversion Nanoparticle Core

[0104] Two-dimensional Ti.sub.3C.sub.2T nanosheets were typically prepared via mixing 1 g of Ti.sub.3C.sub.2Al Max phase in 10 mL HF (48%) with stirring for 24 h at room temperature to chemically erode the Al metal. The as-obtained NaYF.sub.4:Yb,Er,Ca nanoparticles as seeds for the epitaxial growth of hexagonal NaYF.sub.4: Yb, Er, Ca@NaYF.sub.4: Yb, Ca UCNPs core-shells nanoparticles. This is achieved by mixing YCl.sub.3, YbCl.sub.3, and Ca(CH.sub.3COOH).sub.2 with final concentration of 0.5 mol L.sup.−1 in oleic acid (10 mL) and 1-octadecene (10 mL) under stirring under N.sub.2, while heating at 150° C., then cooled down to 80° C. before the addition of NaYF.sub.4: Yb, Er, Ca core (2 mmol) in cyclohexane (10 mL) then heating to 150° C. without N.sub.2. Following that, CH.sub.3OH (15 mL) involving NH.sub.4F (6 mmol) and NaOH 3.5 mmol) for 20 min under stirring at 50° C. under N.sub.2 for 30 min. The solution was degassed while heating at 150° C. and then heated to 300° C. under N.sub.2 and kept for 2 h 2 h before being cooled to room temperature followed by centrifugation at 10000 rpm and washing by ethanol for 3 times.

Example 3: Synthesis of Multidimensional Multilayered Star-Like Nanoarchitectonics

[0105] Chitosan hydrogel was initially prepared via dissolving chitosan (4 g) in aq. acetic acid (20% v/v, 100 mL) with mechanical stirring at room temperature. Activated Ti.sub.3C.sub.2T.sub.x nanosheets (1 g in 5 mL DDI-H.sub.2O) were added dropwise into the chitosan hydrogel with mechanical stirring and then sonication to remove any air bubbles. The obtained hydrogel was casted onto a glass plate using a doctor blade (drawdown thickness up to 2 mm) for 1 min. The casted membrane was dried in an oven under vacuum at 40° C. for 24 h. The dried membrane was neutralized with NaOH solution and then dried under air 40° C. before any further use or characterization.

Example 4: Synthesis of Multidimensional Multilayered Sandglass-Like Nanoarchitectonics

[0106] The as-obtained hexagonal NaYF.sub.4: Yb, Er, Ca@NaYF.sub.4: Yb, Ca UCNPs core-shells nanoparticles were used as seeds for the epitaxial growth of sandglass-like nanoarchitectonics. This is achieved by mixing YbCl.sub.3, and Ca(CH.sub.3COOH).sub.2 with final concertation of 0.5 mol L.sup.−1 in oleic acid (14 mL), and 1-octadecene (32 mL) contains NdCl.sub.3, (2.5 mol L.sup.−1) under stirring under N.sub.2, while heating at 150° C. under N.sub.2, then cooled down to 80° C. before the addition of NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4: Yb,Ca UCNPs core-shell (2 mmol) in cyclohexane (20 mL). Following that, the reaction solution was heated to 150° C. without N.sub.2, before the addition of CH.sub.3OH (20 mL) involving containing NH.sub.4F (8 mmol) and NaOH (5 mmol) for 20 min under stirring at 50° C. under N.sub.2 for 30 min. The solution was degassed while heating at 150° C. and then heated to 300° C. under N.sub.2 and kept for 2 h before being cooled to room temperature followed by centrifugation at 10000 rpm and washing by ethanol for 3 times. The concentration of NdCl.sub.3 (2.5 mol L.sup.−1) was changed to (2.0 mol L.sup.−1), (1.5 mol L.sup.−1), (1 mol L.sup.−1), (5 mol L.sup.−1) to allow the formation of sandglass nanoarchitectonics with Nd of 10, 20, 40, 60, and 80% respectively.

Example 5: Properties of Multilayered Multidimensional Compositions

[0107] The properties of the materials developed were investigated further as described below and in the accompanying figures.

[0108] FIG. 1A shows the 3D model for the as-developed multidirectional multilayered sandglass-like nanoarchitectonics. FIG. 1B shows the TEM image of sandglass-like nanoarchitectonics NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4: Yb,Ca@NaNdF.sub.4:Yb composed of semi spherical core NaYF.sub.4:Yb,Er,Ca coated with hexagonal core-shell NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4: Yb,Ca coated with outer layer NaNdF.sub.4: Yb of sandglass-like spatial. The average diameter of thus obtained sandglass-like nanoarchitectonics is about 60±4 nm (FIG. 1B). FIG. 1C shows the ICP-OES composition of sandglass nanoarchitectonics, which revealed the presence of Na, Y, Nd, Yb, Er, Ca, and F along with the high atomic content of Nd.sup.−1 (90.05).

[0109] FIG. 2A shows the 3D model for the as-developed multidirectional multilayered star-like nanoarchitectonics. FIG. 2B shows the TEM image of sandglass-like nanoarchitectonics NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4: Yb,Ca@NaNdF.sub.4:Yb composed of semispherical core NaYF.sub.4:Yb,Er,Ca coated with hexagonal core-shell NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4: Yb,Ca coated with outer layer NaNdF.sub.4: Yb of sandglass-like spatial. The average diameter of thus obtained sandglass-like nanoarchitectonics is about 55±3 nm (FIG. 2B). FIG. 2C shows the ICP-OES composition of sandglass nanoarchitectonics, which revealed the presence of Na, Y, Nd, Yb, Er, Ca, and F along with the high atomic content of Nd.sup.−1 (80.1).

[0110] FIG. 3A shows the 3D model for the as-developed core-shell hexagonal nanoarchitectonics. FIG. 3B shows the TEM image of hexagonal core-shell nanoarchitectonics NaYF.sub.4:Yb,Er,Ca@NaYF.sub.4:Yb,Ca composed of semispherical core NaYF.sub.4:Yb,Er,Ca coated with hexagonal core-shell NaYF.sub.4:Yb,Er,Ca. The average diameter of thus obtained sandglass-like nanoarchitectonics is about 28 nm±2 nm (FIG. 3B). FIG. 3C shows the ICP-OES composition of sandglass nanoarchitectonics, which revealed the presence of Y, Yb, and Er along with almost similar atomic (31%) content and with Ca 5.8%.

[0111] FIG. 4A shows the 3D model for the as-developed semispherical core nanoarchitectonics. FIG. 4B shows the TEM image of semispherical core nanoarchitectonics composed of NaYF.sub.4:Yb,Er,Ca. The average diameter of thus obtained sandglass-like nanoarchitectonics is about 14 nm±1 nm (FIG. 4B). FIG. 4C shows the ICP-OES composition of sandglass nanoarchitectonics, which revealed the presence of Y, Yb, and Er along with almost similar atomic (32.5%) content and with Ca (1.9%).

[0112] FIG. 5A shows XRD diffraction patterns of the as-synthesized sandglass-like nanoarchitectonics, which showed the main diffraction patterns of NaNdF.sub.4 with major peaks assigned to {311}, {110} and {100} planes along with some NaYF.sub.4 peaks. FIG. 5B displays the XPS survey of the as-synthesized sandglass-like nanoarchitectonics, which depicted the presence of Y 3d, Er 4d, Yb 4d, C 1s, Na KLL, O 1 s, F 1s, Nd 3, F KLL, and Na 1s spectra indicated the formation of multilayered nanoarchitectonics. FIG. 5C shows upconversion luminescence (UCL) of the as-synthesized sandglass-like nanoarchitectonics, which exhibited multimission peaks assigned to green emission at 522 of (.sup.4H.sub.11/2.fwdarw..sup.4I.sub.15/2) and 542 nm of (.sup.4S.sub.3/2.fwdarw..sup.4I.sub.15/2) along with a red emission peak at 654 nm of (.sup.4F.sub.9/2.fwdarw..sup.4I.sub.15/2) transition. FIG. 5D shows the absorbance of the as-synthesized sandglass-like nanoarchitectonics, which showed the multiple absorption peaks from 500 nm to 900 nm. The maximum absorption was achieved ta 580, 750, 800, and 860 nm.

[0113] FIG. 6A shows the absorbance of the as-synthesized sandglass-like nanoarchitectonics, which showed the multiple absorption peaks from 500 nm to 900 nm. The maximum absorption was achieved ta 580, 750, 800, and 860 nm. FIG. 6a shows XRD diffraction patterns of the as-synthesized star-like nanoarchitectonics, which showed the main diffraction patterns of NaNdF.sub.4 with major peaks assigned to {311}, {110} and {100} planes along with some NaYF.sub.4 peaks. FIG. 6B displays the XPS survey of the as-synthesized star-like-like nanoarchitectonics, which depicted the presence of Y 3d, Er 4d, Yb 4d, C 1s, Na KLL, O 1s, F 1s, F KLL, Nd 3d, and Na 1s spectra indicated the formation of multilayered nanoarchitectonics. FIG. 6C shows upconversion luminescence (UCL) of the as-synthesized star-like nanoarchitectonics, which exhibited multimission peaks assigned to green emission at 522 of (.sup.4H.sub.11/2.fwdarw..sup.4I.sub.15/2) and 542 nm of (.sup.4S.sub.3/2.fwdarw..sup.4I.sub.15/2) along with a red emission peak at 654 nm of (.sup.4F.sub.9/2.fwdarw..sup.4I.sub.15/2) transition.

[0114] FIG. 7A shows XRD diffraction patterns of the as-synthesized hexagonal core-shell nanoarchitectonics, which showed the main diffraction patterns of NaYF.sub.4 peaks. FIG. 7B displays the XPS survey of the as-synthesized hexagonal core-shell nanoarchitectonics, which depicted the presence of Y 3d, Er 4d, Yb 4d, C 1s, Na KLL, O 1s, F 1s, F KLL, and Na 1s spectra indicated the formation of multilayered nanoarchitectonics. FIG. 7C shows upconversion luminescence (UCL) of the as-synthesized hexagonal core-shell nanoarchitectonics, which exhibited multisession peaks assigned to green emission at 522 of (.sup.4H.sub.11/2.fwdarw..sup.4I.sub.15/2) and 542 nm of (.sup.4S.sub.3/2.fwdarw..sup.4I.sub.15/2) along with a red emission peak at 654 nm of (.sup.4S.sub.3/2.fwdarw..sup.4I.sub.15/2) transition.

[0115] FIG. 8A shows XRD diffraction patterns of the as-synthesized semispherical core nanoparticles, which showed the main diffraction patterns of NaYF.sub.4 peaks. FIG. 8B displays the XPS survey of the as-synthesized hexagonal core-shell nanoarchitectonics, which depicted the presence of Y 3d, Er 4d, Yb 4d, C 1s, Na KLL, O 1s, F 1s, F KLL, and Na 1s spectra. FIG. 8C shows upconversion luminescence (UCL) of the as-synthesized semispherical core nanoparticles, which exhibited multisession peaks assigned to green emission at 522 of (.sup.4H.sub.11/2.fwdarw..sup.4I.sub.15/2 and 542 nm of (.sup.4S.sub.3/2.fwdarw..sup.4I.sub.15/2) along with a red emission peak at 654 nm of (.sup.4F.sub.9/2.fwdarw..sup.4I.sub.15/2) transition.

Example 6: Photocatalytic Phenol Degradation

[0116] The photocatalytic phenol degradation process was carried out using the advanced oxidation process using the photochemical reactor (Toption instrument Co. LTD, China), potentiostat (Gamry, USA), electrochemical oxidation reactors. An aqueous solution (100 mL) contains 5 mg/L of phenol was under magnetic stirring at room temperature in the presence of 0.1 g of photocatalysts (contain 0.1% of upconversion) in a dark chamber followed by illumination with a 150 W Xenon lamp (12 mW cm′). Then 3 mL of water were withdrawn every 8 min, filtered using a Whatman nylon filter paper (0.2 μm), and its absorbance was recorded using UV-vis spectra at 269 nm. The degradation percentage (D.sub.100) of phenol was calculated using this equation “D.sub.100=[(C.sub.0−C.sub.t)/C.sub.o]×100” where C.sub.0 and C.sub.t are initial concentration and concentration after time, respectively.

[0117] For the measurements under ozone, the ozone was in situ generated electrochemically using a SiO.sub.2/Ti.sub.3 00nm/Pt100 nm/TiOx100 nm/SnOx500 nm electrode in an aqueous solution 0.5 M NaOH at 8 V, 3000 mA and ozone concertation was monitored using (Ecosensors & 2B Technologies, USA).

[0118] The phenol photocatalytic degradation was carried out on the as-synthesized photocatalysts in the presence and in the absence of H.sub.2O.sub.2 (FIG. 9 to FIG. 16). All experiments were performed using 0.1 g of TiO.sub.2 as support and 0.1% of the upconversion as a photocatalyst. In the presence of H.sub.2O.sub.2, only 70 μl of H.sub.2O.sub.2. The results were compared to commercial TiO.sub.2.

[0119] Table 1 provides a comparison between some photocatalysts of the present invention and previously reported photocatalysts with and without upconversion nanoparticles or elements. The results displayed the superior photocatalytic phenol degradation performance of the upconversion than that of TiO.sub.2, as indicated by the greater degradation percentage under the same conditions (Table 1). In addition, the performance of the upconversion photocatalyst without using H.sub.2O.sub.2 was significantly higher than that of using H.sub.2O.sub.2 (Table 1). It should be noticed that the photocatalytic performance of thus synthesized upconversion photocatalysis was substantially higher than that of all previously reported photocatalysis (Table 1).

TABLE-US-00002 TABLE 1 Photocatalyst Comparison Phenol (concentration Time Degradation Sample (mg/L) (min) (%) Ref. Sandglass-like Xenon lamp 20 mg/L 35 90.21739 Embodiment of upconversion Nd 90% 350 nm invention Without H.sub.2O.sub.2 Sandglass-like Xenon lamp 20 mg/L 35 81.63265 Embodiment of upconversion Nd 80% 350 nm invention Sandglass-like Without 20 mg/L 35 78.84615 Embodiment of upconversion Nd 60% H.sub.2O.sub.2 invention NaYF.sub.4:Yb/Tm@TiO.sub.2/RGO 2 W 980 nm 20 mg/L 12 h (20/5) A (5) laser Er.sup.3+-doped Bi.sub.2WO.sub.6 Xe lamp 20 mg/L 180 min 15% B (500 W) Er.sup.3+-doped Bi.sub.2WO.sub.6 3 W LED 20 mg/L 60 h 40% B NaYF.sub.4:Yb/Tm@TiO.sub.2 980 nm .sup. 20 mg/10 ml 1 h 17% C laser TiO.sub.2 Yb(1.0 mol %) Visible  0.21 mM/5.0 mL 3 h 89% D irradiation (>450 nm) TiO.sub.2 Y(0.25) HT UV-vis 0.21 mM/25 mL 1 h 3.85 E irradiation TiO.sub.2 Y(0.5) SG vis 0.21 mM/25 mL 1 h 0.26 E irradiation (>420 nm) Er.sup.3+:Y.sub.3A.sub.15O.sub.12/Bi.sub.2WO.sub.6 500 W Xe 20 mg/L 2 h 51.0%   F lamp Er.sup.3+ doped Bi.sub.2MoO.sub.6 350 W Xe 20 mg/L 2 h 46.4%   G nanosheets lamp TiO.sub.2 Er (2 mol %) UV-vis- 30 ppm 2 h  6% H NIR Ho—TiO.sub.2 nanotube visible light 30 ppm 1 h 30% I (LEDs max = 465 nm) 2%Er.sup.3+—TiO.sub.2 UV-vis-NIR 30 ppm 2 h 90% J Doping Er.sup.3+ and YAlO.sub.3 into visible-light 0.6 mg/L 16 h 99.8%   K TiO.sub.2 (VPCB) Doping Er.sup.3+ and YAlO.sub.3 into UV light 0.6 mg/L 16 h 67.2%   K TiO.sub.2 (UPCB) NaYF.sub.4:Yb.sup.3+, Tm.sup.3+/g-C.sub.3N.sub.4 980 nm 50 ppm 12 h 50% L (NYT/C.sub.3N.sub.4)-15 wt % laser irradiation

[0120] For Table 1, “A” corresponds to W. Wang et al., Applied Catalysis B: Environmental, 2016,182, 184-192. “B” corresponds to Z. Zhang et al., Applied Catalysis B: Environmental, 2010,101, 68-73. “C” corresponds to W. Wang et al., Applied Catalysis B: Environmental, 2014,144, 379-385. “D” corresponds to J. Reszczyliska et al., Applied Catalysis B: Environmental, 2015,163, 40-49. “E” corresponds to J. Reszczyliska et al., Applied Catalysis B: Environmental, 2016,181, 825-837. “F” corresponds to Z. Zhang et al., Catalysis Communications, 2011,13, 31-34. “G” corresponds to T. Zhou et al., Applied Catalysis B: Environmental, 2011,110,221-230. “H” corresponds to S. Obregon et al., Journal of catalysis, 2013,299, 298-306. “I” corresponds to P. Mazierski et al., Applied Catalysis B: Environmental, 2017,205, 376-385. “J” corresponds to S. Obregon and G. Colon, Chemical communications, 2012,48, 7865-7867. “K” corresponds to D. Zhou et al., Environmental science & technology, 2015,49, 7776-7783. “L” corresponds to M.-Z. Huang et al., Journal of colloid and interface science, 2015,460, 264-272.

[0121] Table 2 provides a comparison of the photocatalytic phenol degradation on the as-synthesized upconversion photocatalysts with and without H.sub.2O.sub.2 compared to commercial TiO.sub.2.

TABLE-US-00003 TABLE 2 Photocatalyst Comparison II Time Degradation (%) Photocatalysts (min) With Using H.sub.2O.sub.2 Commercial TiO.sub.2 35 71.70266 Star-like upconversion 35 94.47514 Octahedral core-shell upconversion 35 86.9281 Hexagonal core-shell upconversion 35 88.55422 Semispherical core upconversion 35 90 Sandglass-like upconversion Nd 90% 35 86.72986 Sandglass-like upconversion Nd 80% 35 82.5 Sandglass-like upconversion Nd 60% 35 72.56637 Sandglass-like upconversion Nd 40% 35 68.99225 Time Degradation (%) Sample (min) Without H.sub.2O.sub.2 Commercial TiO.sub.2 35 56.39535 Star-like upconversion 35 87.05882 Semispherical core upconversion 35 81.01266 Hexagonal core-shell upconversion 35 73.40426 Star-like upconversion Nd 80% 35 83.5443 Sandglass-like upconversion Nd 90% 35 90.21739 Sandglass-like upconversion Nd 80% 35 81.63265 Sandglass-like upconversion Nd 60% 35 78.84615 Sandglass-like upconversion Nd 40% 35 88.60759 UCCK's Core-Shell 35 79.20792

[0122] All publications, patents, and patent applications mentioned in this specification are indicative of the level of skill of those skilled in the art to which the invention pertains, and they are herein incorporated by reference to the same extent as if each were set forth in full.

[0123] The previous detailed description is of a small number of embodiments for implementing the invention and is not intended to be limiting in scope. One of skill in this art will immediately envisage the methods and variations used to implement this invention in other areas than those described in detail. The following claims set forth a number of the embodiments of the invention disclosed with greater particularity.