WO2012151407A1 - Titanium dioxide photocatalytic compositions and uses thereof - Google Patents

Titanium dioxide photocatalytic compositions and uses thereof Download PDF

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Publication number
WO2012151407A1
WO2012151407A1 PCT/US2012/036337 US2012036337W WO2012151407A1 WO 2012151407 A1 WO2012151407 A1 WO 2012151407A1 US 2012036337 W US2012036337 W US 2012036337W WO 2012151407 A1 WO2012151407 A1 WO 2012151407A1
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WIPO (PCT)
Prior art keywords
titanium dioxide
zinc
nanoparticles
photocatalytic
ratio
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PCT/US2012/036337
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English (en)
French (fr)
Inventor
Stewart Benson AVERETT
Devron R. Averett
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Priority to BR112013028330-0A priority Critical patent/BR112013028330B1/pt
Priority to EP12779504.5A priority patent/EP2704825B1/en
Priority to JP2014509443A priority patent/JP6066998B2/ja
Priority to SI201232043T priority patent/SI2704825T1/sl
Priority to NZ618227A priority patent/NZ618227A/en
Priority to MX2013012804A priority patent/MX345457B/es
Priority to AU2012250741A priority patent/AU2012250741B2/en
Priority to ES12779504T priority patent/ES2961392T3/es
Priority to CN201280030858.1A priority patent/CN103608108A/zh
Priority to MX2016013545A priority patent/MX388775B/es
Priority to CA2834798A priority patent/CA2834798C/en
Application filed by Individual filed Critical Individual
Priority to BR122019017167-0A priority patent/BR122019017167B1/pt
Priority to KR1020137032211A priority patent/KR101782540B1/ko
Priority to EP23188893.4A priority patent/EP4299176A3/en
Publication of WO2012151407A1 publication Critical patent/WO2012151407A1/en
Priority to IL229143A priority patent/IL229143A/en
Anticipated expiration legal-status Critical
Priority to ZA2013/08901A priority patent/ZA201308901B/en
Priority to IL248710A priority patent/IL248710B/en
Priority to AU2017200409A priority patent/AU2017200409B2/en
Ceased legal-status Critical Current

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    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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Definitions

  • the present disclosure relates to novel photocatalytic compositions comprising titanium dioxide (Ti0 2 ) nanoparticles, which are useful in the treatment of microbial diseases, more specifically, microbial diseases in plants.
  • Nanoscience vol. 12( 1 ), pgs. 1 -6, 2007; Zhang et al., Journal of Inorganic Materials, vol. 23( 1 ), pgs. 55-60, 2008; and Cui et al., NSTI-Nanotech, vol. 2, pgs. 286-289, 2009).
  • Nanoscale Ti0 2 absorbs light in the UV range, but has very little absorbance in the visible range; this characteristic makes it a useful component in applications where protection from UV damage is helpful. However, in some applications it would be preferable to achieve the photocatalytic effect with longer wavelength light. For example, interior lighting generally exhibits minimal UV energy, greatly reducing the ability of nanoscale Ti0 2 to exhibit photocatalysis.
  • the present disclosure relates to photocatalytic compositions comprising doped titanium dioxide ( ⁇ (3 ⁇ 4) nanoparticles, which are useful in the treatment and prevention of microbial diseases and infestations, more specifically, microbial diseases and infestations in plants.
  • the invention provides a photocatalytic composition comprising titanium dioxide (T1O2) nanoparticles doped with zinc (Zn) and having a ratio of titanium dioxide to zinc from about 5 to about 150.
  • the photocatalytic composition can further comprise silicon dioxide
  • the ratio of titanium dioxide to silicon dioxide is from about 1 to about 500.
  • the titanium dioxide nanoparticles preferably have an average particle size of from about 2 nm to about 20 nm.
  • the photocatalytic compositions absorb electromagnetic radiation in a wavelength range from about 200 nm to about 500 nm, and the absorbance of light of wavelengths longer than about 450 nm is less than 50% the absorbance of light of wavelengths shorter than about 350 nm.
  • the present invention provides for a method for preventing or treating microbial diseases and infestations in plants comprising applying the photocatalytic compositions taught herein to the surface of a plant.
  • the present invention also provides for a method for crop-protecting and yield-enhancing of a plant comprising applying the photocatalytic compositions taught herein to the surface of the plant.
  • Figure 1 is a graphic representation of solar energy capture of various
  • Figure 2 is a graphic representation of the photocatalytic activity of various T1O 2 compositions when irradiated at 354 nm.
  • Figure 3 shows photocatalytic killing of Xanthomonas perforans on surfaces treated with various T1O2 compositions using UV-A light.
  • Figure 4 shows the effectiveness of various T1O2 compositions in preventing/reducing the number of leaf spot lesions per plant in sunlight.
  • Figure 5 shows the effectiveness of selected treatments for the control of olive knot in sunlight.
  • Figure 6 shows the effect of various Ti0 2 compositions on conidial development of Sphaerotheca f liginealEiysiphe cichoracearu , the fungal causal agent of powdery mildew, under sunlight.
  • the invention provides modified photocatalytic compositions that fulfill the requirement for a broadly useful photocatalytic product for use on plants, and demonstrate superiority over unmodified nanoscale T1O 2 . Further, the appropriate application rates have been evaluated.
  • the compositions prevent black leaf spot on tomato plants, increase the yield of marketable fruit, reduce powdery mildew conidia formation on cantaloupe, and protect olive plants from microbially- induced tumors.
  • the compositions contain only well characterized and safe materials, and can be easily appl ied in the field using ordinary spray equipment.
  • the improvements embodied in this invention afford the benefits of photocataiytic activity in settings of low UV irradiance, including interior artificial lighting.
  • the present invention relates to a photocataiytic composition comprising zinc (Zn) doped titanium dioxide (Ti0 2 ) nanoparticles, which is useful in the treatment and prevention of microbial diseases and infestations, more specifically, microbial diseases in plants.
  • the invention provides a photocataiytic composition
  • a photocataiytic composition comprising titanium dioxide (T1O2) nanoparticles doped with zinc (Zn) having a ratio of titanium dioxide to zinc from about 5 to about 1 50.
  • the ratio of titanium dioxide to zinc is preferably from about 40 to about 100.
  • the photocataiytic composition can further comprise silicon dioxide
  • the ratio of titanium dioxide to silicon dioxide is from about 1 to about 500, preferably from about 3 to about 20.
  • the titanium dioxide nanoparticles preferably have an average particle size of from about 2 nm to about 20 nm.
  • a particularly preferred embodiment of the present invention provides a photocataiytic composition which comprises:
  • the photocataiytic composition absorbs electromagnetic radiation in a wavelength range from about 200 nm to about 500 nm, and the absorbance of l ight of wavelengths longer than about 450 nm is less than 50% the absorbance of light of wavelengths shorter than about 350 nm.
  • Another embodiment of the present invention provides for a method for treating or preventing microbial diseases and infestations in a plant comprising applying a photocataiytic composition comprising titanium dioxide (Ti ( 3 ⁇ 4) nanoparticles doped with zinc (Zn) having a ratio of titanium dioxide to zinc from about 5 to about 150, to the surface of a plant.
  • a photocataiytic composition comprising titanium dioxide (Ti ( 3 ⁇ 4) nanoparticles doped with zinc (Zn) having a ratio of titanium dioxide to zinc from about 5 to about 150, to the surface of a plant.
  • Examples of plants to be treated include, but are not limited to, crop plants, which includes herbaceous and woody crop plants, for example, tomato plants, cucumber plants, citrus plants, olive and other drupe plants, apple and other pome plants, nut plants, and ornamental plants.
  • Examples of microbial diseases include, but are not limited to, leaf spot disease, olive knot, fire blight, walnut blight, cherry canker, and powdery mildew.
  • the present invention also provides for a method for increasing crop yield of a plant comprising applying a photocatalytic composition comprising titanium dioxide (T1O2) nanoparticles doped with zinc (Zn) having a ratio of titanium dioxide to zinc from about 5 to about 150, to the surface of a plant.
  • a photocatalytic composition comprising titanium dioxide (T1O2) nanoparticles doped with zinc (Zn) having a ratio of titanium dioxide to zinc from about 5 to about 150, to the surface of a plant.
  • the present invention also provides for a method for treating or preventing microbial disease or infestation on a surface comprising applying a photocatalytic composition comprising titanium dioxide (T1O2) nanoparticles doped with zinc (Zn) having a ratio of titanium dioxide to zinc from about 5 to about 150, to a surface illuminated by artificial light.
  • a photocatalytic composition comprising titanium dioxide (T1O2) nanoparticles doped with zinc (Zn) having a ratio of titanium dioxide to zinc from about 5 to about 150, to a surface illuminated by artificial light.
  • surface means an inanimate or an animate object including plants.
  • the invention provides for a method for treating or preventing microbial diseases or infestations in a plant comprising applying a photocatalytic composition comprising titanium dioxide (Ti(3 ⁇ 4) nanoparticles doped with at least one doping agent, wherein the addition of the doping agent increases the absorbance of light across the range of about 200 nm to about 500 nm, and wherein the absorbance of light of wavelengths longer than about 450 nm is less than 50% the absorbance of light of wavelengths shorter than about 350 nm, to the surface of a plant.
  • the addition of the doping agent increases the absorbance of light across the range of about 350 nm to about 450 nm.
  • the doping agent useful in the photocatalytic composition is selected from the group consisting of Ag, Zn, Si, C, N, S, Fe, Mo, Ru, Cu, Os, Re, Rh, Sn, Pt, Li, Na, and K, and combinations thereof.
  • Particularly preferred doping agents are Zn, Si, and Ag.
  • the invention provides for a photocatalytic composition which absorbs electromagnetic radiation in a wavelength range from about 200 nm to about 500 nm, and the absorbance of light of wavelengths longer than about 450 nm is less than 50% the absorbance of light of wavelengths shorter than about 350 nm.
  • the composition comprises titanium dioxide nanoparticles doped by at least one doping agent, wherein the doping agent disrupts the crystal lattice structure of the titanium dioxide nanoparticles thereby altering the absorbance spectrum of the composition.
  • the invention provides photocatalytic materials that absorb an increased proportion of available electromagnetic energy in a wavelength range that is selected to not substantially interfere with photosynthesis.
  • the utility of the present invention is not l imited to agricultural uses, since improved uti l ization of the energy of light of wavelengths below 500 nm can afford benefit in a variety of settings.
  • the invention is not limited to any particular theory or mechanism of photocatalytic benefit, since photocatalysis may provide benefit by multiple mechanisms, and we do not limit the invention to a particular composition or type of photocatalyst.
  • the synthetic methods used to manufacture such materials may be varied, and we do not limit the invention as to a particular mode of manufacture.
  • At least one means one or more and thus includes individual components as well as mixtures/combinations.
  • doped or “doping” as used herein are understood to encompass the introduction of one or more impurities (e.g., dopant, doping agent) into a material for the purpose of modifying the properties of the material.
  • impurities e.g., dopant, doping agent
  • treatment and “treating” include mitigation of a preexisting microbial disease or infestation.
  • prevention and "prophylaxis” incl ude reduction of the incidence or severity of disease or infestation in either individuals or populations.
  • prophylaxis incl ude reduction of the incidence or severity of disease or infestation in either individuals or populations.
  • nanoscale Ti0 2 Absorption characteristics of nanoscale Ti0 2 were compared to nanoscale Ti0 2 doped with two differing zinc levels and Si0 2 , over the wavelength range of 350 nm to 500 nm.
  • the nanoparticle compositions were manufactured by a modified sol-gel process, to produce formulations containing nanopaiticles of anatase Ti0 2 whose average size was 6 to 7 nm.
  • Zinc was incorporated as a doping agent to provide either low zinc content (0.125% relative to Ti0 2 ) or high zinc content (1 .25% relative to Ti0 2 ). When Si0 2 was an additional dopant, it was present at 10% relative to Ti0 2 .
  • the preparations were dried and absorbance was measured using standard methods for obtaining diffuse reflectance spectra (DRS) of powders.
  • DRS diffuse reflectance spectra
  • the solar irradiance (hemispherical, 37 degree tilt) from ASTM G 173-03 across this spectral range is shown for reference. (See Figure 1 ).
  • the Ti0 2 preparations doped with hetero-atoins absorb more strongly than otherwise similar undoped T1O2 in the near- UV and violet region of the spectrum.
  • the doped preparations absorb 25 to 35 percent more of the energy available from 400 to 450 nm, a region where solar irradiance is relatively high but still outside the main photosynthetic action spectrum of plants.
  • Example 2 Photocatalytic activity of various formulations of TiO? doped with Zn and SiO ⁇ under UV illumination.
  • Example 1 The four formulations described in Example 1 were tested for their photocatalytic activity in a standardized system. Each preparation was suspended in water at approximately 8000 ppm and applied to a glass panel using a robotic high volume low pressure sprayer, and allowed to dry for 24 hours. These panels were each attached to a glass tube to form a container, into which was placed 30 ml of an aqueous solution of methylene blue at a concentration providing an optical density of 2.3 at 664 nm. The tubes were covered with a glass panel and subjected to illumination at an energy density of approximately 0.5 mW/cm 2 from a lamp (GE item F18T8/BLB) affording ultraviolet illumination at 354 nm. This lamp provides no light at wavelengths below 300nm or above 400 nm. The optical density of the methylene blue solution in each sample was monitored over a period of 48 hours and is shown in Figure 2.
  • a lamp GE item F18T8/BLB
  • Example 3 Photocatalytic activity of various formulations of TiO? doped with Zn and SiO ⁇ under visible light illumination.
  • Example 1 The four formulations described in Example 1 were tested for their photocatalytic activity in a second system, in which the experimental illumination was changed to more closely mimic relevant illumination such as daylight or interior light, which are deficient in the ultraviolet energy used in Example 2.
  • the nanoparticle formulations were evaluated as colloidal suspensions in 20 mM phosphate buffer, pH 7.2, rather than on a static surface. The experiment was performed in a 96-well plate format, in which each well contained methylene blue (observed OD655 ranging from 0.05 to 0.5) and a nanoparticle formulation or appropriate controls in a final volume of 200 microliters.
  • the plate was illuminated from a distance of 20 cm with light from two Sylvania Gro-Lux lamps (F20 T12 GRO/AQ). These lamps emit only 2% of their total emitted energy below 400 nm, whereas approximately 36% of their total energy is emitted between 380 and 500 nm, with a peak at 436 nm (reference: Technical Information Bulletin "Spectral Power Distributions of Sylvania Fluorescent Lamps", Osram Sylvania, vvvvw.sylvania.com).
  • compositions of the four preparations tested in this experiment were independently verified by the analytical technique known as ICP-AES
  • Example 4 Photocatalytic killing of the plant pathogen Xanthomonas perforans on a surface using incandescent liaht.
  • Sterile glass cover slips were separately coated with 0.5 ml volumes of one of several types of nanoparticle suspensions (Ti0 2 , Ti0 2 /Ag or Ti(3 ⁇ 4/Zn).
  • the nanoparticle compositions comparable to those in Example 2, were manufactured by a modified sol-gel process, to produce formulations containing nanoparticles of anatase T1O2 whose average size was 6 to 7 nm, and which were doped with cither Ag or Zn, using a ratio of Ti0 2 to dopant of approximately 400: 1 and approximately 800: 1 respectively.
  • the coverslips were dried under sterile conditions.
  • Xanthomonas perforans was applied to treated and untreated coverslips.
  • the coverslips were then either illuminated with incandescent light at an illumination density of 3 x 10 4 lux or maintained in a dark environment.
  • coverslips were placed in sterile centrifuge tubes containing 10 ml of sterile water and vortexed.
  • the recovered bacteria were collected by centrifiigation (14000 x g, 3 minutes) and suspended in 1 ml of sterile water.
  • the numbers of viable bacteria in the resulting suspensions were enumerated by standard plate dilution methods. The results are shown in Figure 3.
  • Example 5 Infection of tomato plants by Xanthomonas perforans, a causative agent of leaf spot, is reduced by treatment with photocatalytic materials.
  • Xanthomonas perforans strain Xp l -7 The infected plants were treated at the 3-4 leaf stage with nanoparticles (Ti0 2 , T i0 2 /Ag & Ti0 2 /Zn) either undiluted or after tenfold dilution.
  • the nanoparticles were suspended in water at concentration of 7,500- 10,000 ppm or 5,000 to 8,000 ppm as indicated in Figure 4.
  • the plants were irrigated daily to keep the soil moisture level at 85-95%, and misted with water two times a day for 15 minutes each to enhance pathogen growth.
  • Three plants were tested for each treatment and the trial was set-up in a randomized complete block design. Bacterial spot lesions were recorded before and two weeks after the treatment. Results are shown in Figure 4.
  • the error bar represents the standard error of the mean.
  • Example 6 Protection from Olive Knot caused by Pseudomoncts syringae py.
  • Olive knot is a disease of olive trees caused by P. syringae pv savastonoi, a motile gram negative bacterium that creates tumors (knots) in olive trees. The organism survives in these knots and is dispersed during wet periods, whereupon it enters new sites via wounds including leaf and flower abscission scars and those induced by mechanical injury from wind, pruning, or frost. These knots inhibit proper plant growth and reduce fruit production. As in many other bacterial diseases of plants, a reduction in the population of bacteria before disease is evident prevents or reduces the occurrence of olive knot, and methods to reduce the bacterial population are thus a common approach in agriculture.
  • the inoculated sites were wrapped with a single layer of Parafilm for one day to maintain enough moisture to ensure high rates of infection, even though this reduced the amount of light at the inoculation site.
  • the ⁇ 0 2 preparation doped with Zn used in the greenhouse experiment was selected for use in a field trial.
  • Zn was selected as the dopant for further investigation due to its approval by the U.S. Environmental Protection Agency as a minimal risk pesticide, a status not accorded other potential doping agents.
  • Field trials were performed to compare the effectiveness of Ti0 2 doped with Zinc at a ratio of 800: 1 (formulated as a 0.7 % colloidal suspension in H 2 0) to standard treatments for prevention or control of leaf spot on tomato plants. Each treatment group contained 48 plants ( 12 per plot, 4 replicates), and the trial used a randomized complete block design.
  • the Ti0 2 /Zn was diluted in water to provide a range of application rates. Controls included a copper sulfate formulation either alone or in conjunction with manzate, and no treatment.
  • X represents the undiluted formulation of ⁇ 2/ ⁇ .
  • X represents the undiluted formulation of Ti(3 ⁇ 4 / Zn.
  • Example 7 The protocol was identical to Example 7, wherein various dilutions of the nanoscale T1O2 /I0W Zn aqueous preparation were applied weekly by conventional high volume, low pressure compressed air spray to tomatoes in the field in a random block design, with appropriate controls.
  • the results for disease progression are presented in Tabic 4, below, and demonstrate a concentration dependent control of disease.
  • yield data are not available for this experiment due to severe damage from a hailstorm prior to fruit harvest.
  • Table 4 Effect of TiCVZn on the incidence of bacterial spot on tomato cultivar ' BtfN 602', shown as average area under the disease progress curve
  • X represents the undiluted formulation of Ti(3 ⁇ 4/Zn. Disease severities were rated using the Horsfall-Barratt scale, a non- dimensional 12-point scale, to assess the percentage of canopy affected by bacterial spot. Values were converted to mid-percentages and used to generate
  • Table 5 Effect of Ti0 2 /Zn on the incidence of bacterial spot on tomato cultivar 'BHN 602', shown as average area under the disease progress curve
  • X represents the undiluted formulation of TiC ⁇ /Zn. Disease seventies were rated using the Horsfall-Barratt scale, a non- dimensional 12-point scale, to assess the percentage of canopy affected by bacterial spot. Values were converted to mid-percentages and used to generate AUDPC.
  • Example 1 0 The effect of ⁇ ?/ ⁇ , formulated as in Examples 7 and 8, on conidial development of Sphaerotheca fiiliginealErysiphe cichoracearum, the fungal causal agent of powdery mildew.

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