Patent Application
20230381756
The present invention is directed to multidimensional upconversion nanomaterial compositions and methods that are useful in the photolytic degradation of phenolic pollutants, such as phenol.
Almost all industries use and release phenol, which is highly toxic to aquatic life, the environment, and humans. Due to the physiochemical stability of phenol to photo-, electro-, photoelectro-, and bio-degradation, its degradation under ambient conditions is a daunting challenge and takes several hours even in the presence of high amounts of catalysts. Likewise, the degradation of phenol using photocatalysts is also a sluggish process, requiring several hours to reach 80% completion, because of the inferior visible light absorption (˜5%) and low light utilization efficiency.
Thus, there is a need for more effective methods for the removal of phenol and similar pollutants under ambient conditions, which could provide improved methods for removal of these contaminants.
The rational design of upconversion nanostructures has much great attention in biomedical applications ranged from bioimaging and sensing to therapy. The controlled fabrication of multidimensional, multilayered upconversion nanoparticles has been reported (albeit rarely), but for biomedical applications. See B. Xu et al., Journal of Materials Chemistry B, 2016, 4, 2776-2784; B. B. Ding et al., Advanced Materials Interfaces, 2016, 3, 1500649; H.-Q. Wen et al., ACS applied materials & interfaces, 2017, 9, 9226-9232; and M. M. Abualrej al et al., Chemical science, 2019, 10, 7591.
A challenge in the fabrication of a multilayered upconversion nanomaterial is its multidimensional nanostructure, which has a tendency to grow in a zero-dimensional shape to reduce total surface energy. The reported upconversion materials may also contain only one sensitizer wth low content, which may make them less suitable for use.
Thus, there is a need for more efficient production of multilayered upconversion compositions.
Provided herein are novel multilayered upconversion nanomaterial compositions and methods.
In certain embodiments, the multidimensional multilayered upconversion nanoarchitectonics has unique structural and compositional merits for photocatalytic degradation of a phenolic pollutant (e.g., phenol) within a few min (˜30±5 min) at room temperature, a rate never reported elsewhere for any photocatalysts. Distinct from traditional photocatalysts (e.g., transition metal oxides, quantum dots, and their hydrides), the present invention's upconversion nanoarchitectonics can maximize the visible light absorption with low energy to higher energy radiation along with great near-infrared (NIR) light adsorption resonant non-radiative transfer. The obtained multilayered nanoarchitectonics involve multiple sanitizers with tunable contents and multidimensional, anisotropic, and outstanding surface merits (branches, cavities, corners) that provide massive adsorption sites for light absorption.
In certain embodiments, the present invention is directed to a multi-layered upconversion nanoparticle including:
In certain embodiments, the present invention is directed to a method for degrading a phenolic pollutant (e.g., phenol) in a medium (e.g., water), the method including exposing a mixture of the medium and the multi-layered upconversion nanoparticle as otherwise disclosed herein to light.
In certain embodiments, the present invention is directed to a method for preparing the multi-layered upconversion nanoparticle as otherwise disclosed herein (e.g., a seed-mediated growth method coupled with a solvothermal method), the method including 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.
Other embodiments and aspects of the invention as described herein and are considered a part of the claimed invention.
Illustrative embodiments of the present invention are described in detail below with reference to the attached drawing figures, which are incorporated by reference herein.
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.
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).
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.
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.
As used herein, “nanoscale” refers to particles having a size of less than 100 nm.
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).
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.
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.
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.
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.
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.
As used herein, “three-dimensional” materials refer to materials where each dimension is outside the nanoscale.
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.
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.
In certain embodiments, this invention is directed to the rational design of novel kind of upconversion nanoarchitectonics materials with tunable Nd content.
This invention also reports a new use for upconversion as photocatalysis along with a substantial improvement of the photocatalytic properties of commercial TiO2 catalyst.
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 (NaYF4:Yb,Er,Ca) in a spherical shape, second layer (NaYF4:Yb,Ca) in a hexagonal shape and exterior layer (NaNdF4:Yb,Ca) in spatial dendritic shape with Nd of (80% w/w).
The invention comprises the synthesis of multilayered, multidimensional upconversion sandglass nanoarchitectonics composed of an active interior (NaYF4:Yb,Er,Ca) in a semispherical shape, an intermediate layer (NaYF4:Yb,Ca) in hexagonal shape, and an outer layer (NaNdF4:Yb,Ca) in sandglass shape with Nd of (10-80% w/w).
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.
The method allows the high-mass production of freestanding or supported nanoarchitectonics with different morphologies and compositions.
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).
The Nd3+ in the outer shell act as a sensitizer and enhance the NIR photons absorption. Meanwhile, Yb3+ in the intermediate layer act as a bridge for energy transfer from Nd3+ to Er3+ activator in the inner core besides avoiding energy back-transfer and quenching from Er3+ and Nd3+, respectively.
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.
In certain aspects and embodiments, provided herein is a multi-layered upconversion nanoparticle including:
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.
In certain embodiments, the active core includes NaYF4:Yb,Er,Ca. In certain embodiments, the active core is NaYF4:Yb,Er,Ca.
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.
In certain embodiments, the intermediate layer includes NaYF4:Yb,Ca. In certain embodiments, the intermediate layer is NaYF4:Yb,Ca.
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.
In certain embodiments, the outer layer includes NaNdF4:Yb. In certain embodiments, the outer layer is NaNdF4:Yb.
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.
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.
In certain aspects and embodiments, provided herein are compositions including hexagonal core-shells nanoparticles. In certain embodiments, the nanoparticles include NaYF4: Yb, Er, Ca@NaYF4: Yb, Ca UCNPs core-shells nanoparticles.
In certain embodiments, the compositions include multidimensional multilayered star-like nanoarchitectonics. In certain embodiments, the composition include multidimensional multilayered sandglass nanoarchitectonics.
Further disclosure is provided containing all the technical descriptions of the invention, including the obtained preparation, characterization, and results.
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
In certain embodiments, provided herein are methods of preparing hexagonal core-shell nanoparticles, including:
In certain embodiments, provided herein are methods of preparing multidimensional multilayered nanoparticles, including:
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.
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.
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.
In certain aspects, provided herein is a method for degrading a phenolic pollutant (e.g., phenol) in a medium, the method including
In certain embodiments, the light is visible light. In certain embodiments, the light is near infrared light (NIR).
In certain aspects and embodiments, provided herein is a method of photolytically degrading a phenolic pollutant (e.g., phenol), including:
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).
In certain embodiments, the method further includes exposing the mixture to near-infrared radiation.
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%).
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 TiO2 alone in the presence and in the absence of H2O2.
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).
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.
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).
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.
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.
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).
In certain embodiments, the degrading pollutants in the medium (e.g., wastewater) occurs at room temperature.
In certain embodiments, the degrading pollutants in the medium (e.g., wastewater) occurs at atmospheric pressure.
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).
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.
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:
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. 5×10−9 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).
All chemicals were used as received without any modifications. Semispherical upconversion NaYF4:Yb,Er,Ca nanoparticles were prepared by mixing YCl3, YbCl3, Ca(CH3COOH)2, and ErCl3 with final concertation of 0.5 mol L−1 in oleic acid (10 mL) and 1-octadecene (10 mL) under stirring under N2, while heating at 150° C., then cooled down to 50° C. before the addition of CH3OH (5 mL) involving NH4F (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 N2 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.
Two-dimensional Ti3C2T nanosheets were typically prepared via mixing 1 g of Ti3C2Al Max phase in 10 mL HF (48%) with stirring for 24 h at room temperature to chemically erode the Al metal. The as-obtained NaYF4:Yb,Er,Ca nanoparticles as seeds for the epitaxial growth of hexagonal NaYF4: Yb, Er, Ca@NaYF4: Yb, Ca UCNPs core-shells nanoparticles. This is achieved by mixing YCl3, YbCl3, and Ca(CH3COOH)2 with final concentration of 0.5 mol L−1 in oleic acid (10 mL) and 1-octadecene (10 mL) under stirring under N2, while heating at 150° C., then cooled down to 80° C. before the addition of NaYF4: Yb, Er, Ca core (2 mmol) in cyclohexane (10 mL) then heating to 150° C. without N2. Following that, CH3OH (15 mL) involving NH4F (6 mmol) and NaOH 3.5 mmol) for 20 min under stirring at 50° C. under N2 for 30 min. The solution was degassed while heating at 150° C. and then heated to 300° C. under N2 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.
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 Ti3C2Tx nanosheets (1 g in 5 mL DDI-H2O) 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.
The as-obtained hexagonal NaYF4: Yb, Er, Ca@NaYF4: Yb, Ca UCNPs core-shells nanoparticles were used as seeds for the epitaxial growth of sandglass-like nanoarchitectonics. This is achieved by mixing YbCl3, and Ca(CH3COOH)2 with final concertation of 0.5 mol L−1 in oleic acid (14 mL), and 1-octadecene (32 mL) contains NdCl3, (2.5 mol L−1) under stirring under N2, while heating at 150° C. under N2, then cooled down to 80° C. before the addition of NaYF4:Yb,Er,Ca@NaYF4: Yb,Ca UCNPs core-shell (2 mmol) in cyclohexane (20 mL). Following that, the reaction solution was heated to 150° C. without N2, before the addition of CH3OH (20 mL) involving containing NH4F (8 mmol) and NaOH (5 mmol) for 20 min under stirring at 50° C. under N2 for 30 min. The solution was degassed while heating at 150° C. and then heated to 300° C. under N2 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 NdCl3 (2.5 mol L−1) was changed to (2.0 mol L−1), (1.5 mol L−1), (1 mol L−1), (5 mol L−1) to allow the formation of sandglass nanoarchitectonics with Nd of 10, 20, 40, 60, and 80% respectively.
The properties of the materials developed were investigated further as described below and in the accompanying figures.
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 (D100) of phenol was calculated using this equation “D100=[(C0−Ct)/Co]×100” where C0 and Ct are initial concentration and concentration after time, respectively.
For the measurements under ozone, the ozone was in situ generated electrochemically using a SiO2/Ti3 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).
The phenol photocatalytic degradation was carried out on the as-synthesized photocatalysts in the presence and in the absence of H2O2 (
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 TiO2, as indicated by the greater degradation percentage under the same conditions (Table 1). In addition, the performance of the upconversion photocatalyst without using H2O2 was significantly higher than that of using H2O2 (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).
20 mg/10 ml
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.
Table 2 provides a comparison of the photocatalytic phenol degradation on the as-synthesized upconversion photocatalysts with and without H2O2 compared to commercial TiO2.
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.
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.
This application is a U.S. non-provisional application that claims the benefit of U.S. Provisional Application No. 63/346,270 (filed May 26, 2022), which is hereby incorporated by reference for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| 63346270 | May 2022 | US |
