PHOTOCATALYTIC HYDROGEN PRODUCTION FROM WATER OVER MIXED PHASE TITANIUM DIOXIDE NANOPARTICLES

Abstract

Photocatalysts and methods of using photocatalysts for synergistic production of hydrogen from water are disclosed. The photocatalysts include photoactive titanium dioxide particles having an anatase to rutile ratio of at least 1.5:1 and electrically conductive material deposited on the titanium dioxide particle.

Claims

1. A photocatalyst comprising: (a) mixed phase titanium dioxide nanoparticles having: a mean particle size of 95 nanometers (nm) or less, and having a ratio of anatase to rutile of at least 1.5:1 to 10:1, and a surface area of 15 m.sup.2/g to 30 m.sup.2/g; and (b) an electrically conductive material deposited on the surface of the titanium dioxide nanoparticles, wherein the electrically conductive material comprises a metal or a metal compound thereof, wherein the mixed phase titanium dioxide nanoparticles are the reaction product of single phase titanium dioxide anatase nanoparticles having a mean particle size of 95 nm or less and heat, and wherein particle size is determined by X-ray Diffraction and surface area is determined using BET analysis.

2. (canceled)

3. The photocatalyst of claim 1, wherein the anatase phase to rutile phase ratio ranges from 1.5:1 to 5:1.

4. The photocatalyst of claim 1, wherein the mean particle size ranges from 10 nm to 80 nm.

5. The photocatalyst of claim 1, wherein the Ti2p.sub.3/2 binding energy as determined by X-Ray PhotoElectron Spectroscopy (XPS) falls in between that of single phase TiO.sub.2 anatase particle and a single phase TiO.sub.2 rutile particle.

6. The photocatalyst of claim 1, wherein the electrically conductive material comprises a metal or a metal compound thereof.

7. The photocatalyst of claim 6, wherein the electrically conductive material comprises silver (Ag), rhodium (Rh), gold (Au), platinum (Pt), palladium (Pd) or any combination thereof.

8. (canceled)

9. The photocatalyst of claim 8, wherein the photocatalyst is Pt.

10. (canceled)

11. The photocatalyst of claim 1, wherein the single phase TiO.sub.2 anatase particles have been heated at a reaction temperature of 740 C. for one hour.

12. The photocatalyst of claim 1, wherein the photocatalyst has photocatalytic activity.

13. The photocatalyst of claim 1, wherein the photocatalyst is capable of catalyzing the production of H.sub.2 from water at an increased rate as compared to production of H.sub.2 from water under the same conditions and using a mixed phase titanium dioxide photocatalyst having a substantially same amount of anatase and rutile phases and a particle size of greater than 100 nm.

14. The photocatalyst of claim 13, wherein the photocatalyst is comprised in a composition that includes the water.

15. The photocatalyst of claim 14, wherein the composition further comprises a sacrificial agent.

16. The photocatalyst of claim 15, wherein the sacrificial agent comprises one or more alcohols, diols, polyols, dioic acids, and any combination thereof.

17. The photocatalyst of claim 15, wherein the sacrificial agent comprises methanol, ethanol, propanol, iso-propanol, n-butanol, iso-butanol, ethylene glycol, propylene glycol, glycerol, or oxalic acid, or any combination thereof.

18. (canceled)

19. (canceled)

20. A method of producing a photocatalyst as in claim 1, comprising: (a) heating single phase titanium dioxide anatase nanoparticles having a mean particle size of 95 nanometers (nm) or less isochronally at a temperature ranging from 700 C. to 800 C. for a desired period of time to produce mixed phase titanium dioxide nanoparticles having a mean particle size of 95 nm or less and a surface area of the mixed phases titanium dioxide nanoparticles ranges from 15 m.sup.2/g to 30 m.sup.2/g, wherein the mixed phase titanium dioxide nanoparticles comprise anatase and rutile phases at a ratio of at least 1.5:1 to 10:1; (b) depositing an electrically conductive material on the surface of the mixed phase titanium dioxide nanoparticles, wherein the electrically conductive material comprises a metal or a metal compound thereof.

21. (canceled)

22. The method of claim 20, wherein the electroconductive material comprises silver (Ag), rhodium (Rh), gold (Au), platinum (Pt), palladium (Pd) or mixtures thereof.

23. The method of claim 20, wherein depositing the electroconductive material comprises contacting the mixed phase TiO.sub.2 nanoparticles with an acidic aqueous solution comprising a salt of the electroconductive material.

24. (canceled)

25. The method of claim 20, further comprising calcining the electroconductive material/mixed phase titanium dioxide anatase nanoparticles after step (b).

26. A system for producing H.sub.2 from H.sub.2O, comprising: (a) a container comprising a mixture of photocatalyst of claim 1, water and a sacrificial agent; and (b) a light source configured to provide light to the mixture.

27. (canceled)

28. A method for producing H.sub.2 from water, comprising: (a) obtaining a system of claim 26; and (b) subjecting the mixture to the light source for a sufficient period of time to produce the H.sub.2 from the water.

29. (canceled)

30. (canceled)

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 is a schematic of the TiO.sub.6 octahedra in anatase and rutile phases along the c-axis.

[0029] FIG. 2A depicts a transmission electron microscopy image of a single phase titanium dioxide anatase microparticle heated for 1 hour at 1000 C.

[0030] FIG. 2B depicts a transmission electron microscopy images of the single phase titanium dioxide anatase microparticle of FIG. 2A after 5 hours of heating at 1000 C.

[0031] FIG. 3 is a schematic of an embodiment of a water-splitting system using the photocatalysts of the invention.

[0032] FIG. 4 are XRD spectra of embodiments of titanium dioxide nanoparticle samples having various amounts of rutile phase.

[0033] FIG. 5 are XRD spectra of titanium dioxide microparticle comparison samples having various amounts of rutile phase.

[0034] FIG. 6 depict UV-Vis spectra of absorbance in Tauc units versus electron volts (eV) of photocatalysts of the invention containing 1 wt. % Pt/TiO.sub.2 nanoparticles with different percentages of rutile.

[0035] FIG. 7 depicts UV-Vis spectra of absorbance in Tauc units versus electron volts (eV) of comparison photocatalysts containing 1 wt. % Pt/TiO.sub.2 microparticles with different percentages of rutile.

[0036] FIG. 8 are XPS spectra of the Pt4f of comparison photocatalysts containing 1 wt. % Pt/TiO.sub.2 microparticle samples.

[0037] FIG. 9 is an XPS spectrum of the Pt4f of photocatalyst of the invention containing 1 wt. % Pt/TiO.sub.2 nanoparticles containing 10% rutile.

[0038] FIG. 10 are XPS spectra of the Ti2p of pure TiO.sub.2 rutile, pure TiO.sub.2 anatase, and photocatalysts of the invention containing mixed phase nanoparticles having various percentages of rutile.

[0039] FIG. 11 depict XPS spectra of the Valence Band region of comparison photocatalysts of pure 1 wt. % Pt/TiO.sub.2 rutile before and after Argon ion sputtering.

[0040] FIG. 12 depict XPS spectra of the Valence Band region of a comparison photocatalysts of 1 wt. % Pt/TiO.sub.2 anatase and photocatalysts of the invention containing mixed phase 1 wt. % Pt/ TiO.sub.2 nanoparticles having various percentages of rutile phase before and after Argon ion sputtering.

[0041] FIG. 13 is a graphical depiction of hydrogen production versus time for photocatalysts of the invention containing 1 wt. % Pt/TiO.sub.2 nanoparticles with increasing rutile content.

[0042] FIG. 14 is a graphical depiction of hydrogen production versus time for comparison photocatalysts of 1 wt. % Pt/TiO.sub.2 microparticles with increasing rutile content.

[0043] FIG. 15 is a graphical depiction of hydrogen production from 1 wt. % Pt/TiO.sub.2 nanoparticles photocatalysts of the invention and 1 wt. % Pt/TiO.sub.2 microparticles comparison photocatalysts versus rutile content.

DETAILED DESCRIPTION OF THE INVENTION

[0044] While hydrogen-based energy from water has been proposed as a solution to the current problems associated with carbon-based energy (e.g., limited amounts and fossil fuel emissions), the currently available technologies are expensive, inefficient, and/or unstable. The present application provides a solution to these issues. The solution is predicated on the use of heat-treated mixed phase titanium dioxide nanoparticles having a mean particle size of 95 nanometers (nm) or less and a ratio of anatase to rutile of at least 1.5:1 as photocatalysts. It has been unexpectedly found that photocatalyst of the invention produces higher amounts of hydrogen in photocatalytic water-splitting reactions than similar photocatalysts made from microparticles. This higher hydrogen production rate is attributed to a synergistic effect between the phase ratio and the particle size of the titanium dioxide nanoparticles.

[0045] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

A. Photoactive Catalysts

[0046] The photocatalyst is composed of titanium dioxide particles having two main polymorphs, anatase and rutile. The particles have different properties and different photocatalytic performance. Combination of these properties provides for a photocatalyst having better physical and electron transfer properties. While anatase and rutile both have a tetragonal crystal system consisting of TiO.sub.6 octahedra, their phases differ in that anatase octahedras are arranged such that four edges of the octahedras are shared, while in rutile, two edges of the octahedras are shared. FIG. 1 is a schematic of the TiO.sub.6 octahedra in anatase and rutile along the c-axis. The shared edges are in bold lines. These different crystal structures may account for the different efficiencies observed for transfer of charge carriers (electrons) in the rutile and anatase phases and the different physical properties of the catalyst. For example, anatase is more efficient than rutile in the charge transfer, but is not as durable as rutile. A more durable photocatalyst may extend the life of the catalyst during use. Without wishing to be bound by theory, it is believed that the when rutile nanoparticles are formed on the surface of the single phase anatase nanoparticles, the electron-hole recombination rate is retarded due to electron transfer from the rutile to the anatase phase. In other words, because the electron-hole recombination rate is fast in rutile and slow in anatase (See, for example, Xu, et al. in Physics Review Letters 2011, Vol. 106, pp. 138302-1 to 138302-4) and because the number of electron and holes is higher in rutile than in anatase at a given wavelength capable of exciting both materials, the mixture performs better in photocatalytic water-splitting reactions. The materials, therefor benefits from a large number of carriers (in rutile) and a slow rate of recombination (in anatase) giving them more time to make the reduction of hydrogen ions to hydrogen molecules and the oxidation of oxygen ions to oxygen molecules. Heat-treating the single phase titanium dioxide anatase nanoparticle produces small particles of rutile on top of anatase particles, thus maximizing the interface between both phases and at the same time allowing for a large number of adsorbates (water and ethanol) to be in contact with both phases, due to the initial small particle size. FIG. 2A depicts a transmission electron microscopy image of a single phase titanium dioxide anatase microparticle heated for 1 hour at 1000 C. FIG. 2B depicts a transmission electron microscopy images of the single phase titanium dioxide anatase microparticle of FIG. 2A after 5 hours of heating at 1000 C. Comparing FIG. 2A to FIG. 2B, an increased amount of TiO.sub.2 rutile phase particles having a size of about 1-2 nm are observed after 5 hours of heating as compared to the number of TiO.sub.2 rutile phase particles observed after 1 hour of heating. Thus, titanium dioxide photocatalysts having various amounts of rutile and anatase extend the life of the catalyst and maximize efficient electron transfer properties.

[0047] In one aspect of the invention, mixed phase titanium dioxide anatase and rutile may be the reaction (transformation) product obtained from heat-treating single phase titanium dioxide anatase at selected temperatures. Single phase TiO.sub.2 anatase nanoparticles can be purchased from various manufacturers and suppliers (e.g., Titanium (IV) oxide anatase nanoparticles in a variety of sizes and shapes can be obtained from Sigma-Aldrich Co. LLC (St. Louis, Mo., USA) and from Alfa Aesar GmbH & Co KG, A Johnson Matthey Company (Germany)); L.E.B. Enterprises, Inc. (Hollywood, Fla. USA)). A surface area of the single phase TiO.sub.2 anatase nanoparticles ranges from about 45 m.sup.2/g to about 80 m.sup.2/g, or from 50 m.sup.2/g to 70 m.sup.2/g, or preferably about 50 m.sup.2/g. The particle size of the single phase TiO.sub.2 anatase nanoparticles is less than 95 nanometers, less than 50 nm, less than 20, or preferably between 10 and 25 nm. Reaction conditions can be varied based on the TiO.sub.2 anatase particle size and/or method of heating (See, for example, Hanaor et al. in Review of the anatase to rutile phase transformation, J. Material Science, 2011, Vol. 46, pp. 855-874), and are sufficient to transform single phase titanium dioxide to mixed phase titanium dioxide anatase and rutile. For example, titanium dioxide anatase can be transformed into a mixed phase polymorph by flame pyrolysis of TiCl.sub.4, solvothermal/hydrothermal methods, chemical vapor deposition, and physical vapor deposition methods. A non-limiting example of transforming nanoparticles of TiO.sub.2 anatase nanoparticles to mixed phase TiO.sub.2 anatase and rutile nanoparticles includes heating single phase TiO.sub.2 anatase nanoparticles isochronally at a temperature of 700-800 C. for about 1 hour to transform the nanoparticles of TiO.sub.2 anatase phase to nanoparticles of mixed phase TiO.sub.2 anatase phase and rutile phase (See, for example FIG. 4 in the Examples). In a preferred embodiment, titanium dioxide anatase is heated to a temperature of 780 C. to obtain mixed phase titanium dioxide containing about 37% rutile. Notably, it was discovered that when mixed phase TiO.sub.2 nanoparticles having a ratio of anatase to rutile of at least 1.5:1 or greater is used as a photocatalyst in water-splitting processes, higher production rates of hydrogen were observed as compared to similar photocatalyst containing mixed phase titanium dioxide microparticles. This higher rate of hydrogen production is attributed to a synergistic effect between the particle size and phase ratio of the titanium dioxide nanoparticles. Without wishing to be bound by theory, it is believed that this ratio and the particle structure may allow for the efficient transfer of charge carriers (electrons) from the rutile phase to the anatase phase, where said charge carries in the anatase phase have an increased chance of being transferred to the metal conducting materials rather than undergoing an electron-hole recombination event. The mixed phase TiO.sub.2 nanoparticles of the present invention can have a ratio of anatase and rutile phase ranges from 1.5:1 to 10:1, from 6:1 to 5:1, or from 5:1 to 4:1. The percentage of anatase to rutile the titanium dioxide polymorph can be determined using powder X-ray diffraction (XRD) techniques. For example, a Philips Xpert-MPD X-ray powder diffractometer may be used to analyze powder samples of titanium dioxide polymorphs. Using the areas of these peaks the amounts of rutile phase in the titanium dioxide polymorph can be determined using the following equation:

[00001]$\begin{array}{cc}\%.Math..Math.\mathrm{rutile}=\frac{1}{\left(\frac{A}{R}0.884\right)+1}100& \left(1\right)\end{array}$ [0048] where A is the area of anatase peak; R is the area of rutile peak as determined by XRD; and 0.884 is a scattering coefficient.

[0049] In an aspect of the invention, it was surprisingly found that the percentage in the change of surface area of mixed phase titanium dioxide anatase and rutile nanoparticles was significantly different than the percentage change in the surface area of the mixed phase titanium dioxide anatase and rutile microparticles relative to the respective starting materials. For example, the surface area of the titanium dioxide microparticles decreased by about 40% at a 25% conversion to rutile phase relative to the surface area of the starting material as determined by Brunauer-Emmett-Teller (BET) methods. In contrast, the surface area of the titanium dioxide nanoparticles decreased by about 70% at a 29% conversion to rutile phase relative to the surface area of the staring material. In particular aspects of the invention, a surface area of the mixed phase TiO.sub.2 nanoparticles may decrease by a factor of at least 0.1, at least 0.4, or at least 0.5. The resulting mixed phase titanium dioxide nanoparticles have a surface area of about 15 m.sup.2/g, or preferably from 15 m.sup.2/g to 30 m2/g. Without wishing to be bound by theory, it is believed that the decrease in the nanoparticle surface area as compared to the microparticle surface area demonstrates that less sintering has occurred on the catalyst surface and a higher degree of crystallinity has been obtained. A higher degree of crystallinity leads to minimum perturbation of the titanium dioxide wave function, which allows enhanced migration of electrons from the bulk portion of the titanium dioxide particle to the surface of the titanium dioxide particle and less recombination of electrons.

[0050] Further, during heating, the particle size of the pure anatase changes from a single modal distribution to a bimodal distribution, where the anatase and rutile phases have different particle sizes. The overall particle size distribution, however, of the resulting TiO.sub.2 remains less than 100 nm. During heat treatment, the particle size of the original anatase phase increases by a factor of at least 1.5, at least 2, or at least 0.45, while the particle size of the formed rutile phase is from about 0 nm to less than 100 nm depending on the temperature used to form the rutile phase (See, for example, the d values for anatase and rutile phases in Table 1 of the Examples). Even though an increase in particles size is observed during heating, the mean particle size of the mixed phase TiO.sub.2 nanoparticles is less than 100 nm. The mixed phased nanoparticles of the invention have a mean particle size of less than 95 nm, from about 10 nm to about 80 nm, from about 15 nm to about 50 nm, from about 20 nm to about 50 nm, or from about 15 nm to about 20 nm.

[0051] In a further aspect of the invention, transforming the single phase TiO.sub.2 anatase to a mixed phase TiO.sub.2 having a anatase to rutile phase ratio of at least 1.5:1 changes the binding energy and the band gap relative to single phase TiO.sub.2 anatase and single phase TiO.sub.2 rutile. This change in binding energy and band gap is believed to allow efficient transfer of charge carriers (electrons) from the rutile phase to the anatase phase, where said charge carries in the anatase phase have an increased chance of being transferred to the metal conducting materials rather than undergoing an electron-hole recombination event. The TiO.sub.2 nanoparticles of the present invention have a Ti2p.sub.3/2 binding energy as determined by X-ray photoelectron spectroscopy (XPS) that is in between that of single phase TiO.sub.2 anatase and single phase TiO.sub.2 rutile. The mixed phase TiO.sub.2 nanoparticles also have a band gap between about 3.0 electron volts (eV) and 3.2 eV.

[0052] Electroconductive material may be deposited on the surface of the mixed phase TiO.sub.2 nanoparticles to increase the photocatalytic activity of the TiO.sub.2. The electroconductive material includes highly conductive materials, making them well suited to act in combination with the photoactive material to facility transfer of excited electrons to hydrogen before an electron-hole recombination event occurs or by increasing the time that such an event occurs. The electroconductive material can also enhance efficiency via resonance plasmonic excitation from visible light, enabling capture of a broader range of light energy. The electroconductive materials include noble metals such as, for example, platinum, gold, silver and palladium as metals or metal salts. Electroconductive material (i.e., platinum, gold, silver, and palladium) can be obtained from a variety of commercial sources in a variety of forms (e.g., solutions, particles, rods, films, etc.) and sizes (e.g., nanoscale or microscale). By way of example, Sigma-Aldrich Co. LLC and Alfa Aesar GmbH & Co KG offer such products. Alternatively, they can be made by any process known by those of ordinary skill in the art. The electrically conducting material may be deposed on the surface of the mixed phase titanium dioxide nanoparticles. Deposition can include attachment, dispersion, and/or distribution of the metal particles on the surface of the photoactive material or TiO.sub.2 particles. A non-limiting example of depositing the electrically conductive material on the photoactive material includes impregnating the mixed phase TiO.sub.2 nanoparticles with a solution of metal salt. Impregnation may include contacting (for example, spraying or mixing) the mixed phase TiO.sub.2 nanoparticles with an acidic aqueous metal salt solution to form a mixture. The mixture may be stirred at a temperature of about 70 C. to 80 C. for about 10 h, 12 h, or longer. After stirring, the water may be evaporated off to form a dry material. The dry material may be calcined at a temperature of 200 C. to 400 C., or preferably at 350 C. for at least 2 h, at least 4 h, or preferably at least 5 h under atmospheric conditions. The resulting TiO.sub.2 photocatalyst has a total electroconductive material content of about 1 wt. % to about 5 wt. % or about 2 wt. % to about 4 wt %.

B. Water-Splitting System

[0053] FIG. 3 is a schematic of an embodiment of water-splitting system 20. Water-splitting system 20 includes container 10, photocatalyst 12, and light source 14. Container 10 can be translucent or even opaque such as those that can magnify light (e.g., opaque container having a pinhole(s)). Photocatalyst 12 includes mixed phase titanium dioxide nanoparticles (shown as single nanoparticle 16) having a ratio of anatase phase to rutile phase of at least 1.5:1, and electroconductive material. Light source 14 is sunlight, a UV lamp, or an Infrared (IR) lamp. An example of a UV light is a 100 Watt ultraviolet lamp with a flux of about 2 mW/cm.sup.2 at a distance of 10 cm. The UV lamp can be used with a 360 nm and above filter. Such UV lamps are commercial available from, for example, Sylvania. Photocatalyst 12 can be used to split water to produce H.sub.2 and O.sub.2. Light source 14 contacts photocatalyst 12, thereby exciting electrons 18 from their valence band 20 to their conductive band 22, thereby leaving corresponding holes 24. Excited electrons 18 are used to reduce hydrogen ions to form hydrogen gas, and holes 24 are used to oxidize oxygen ions to oxygen gas. The hydrogen gas and the oxygen gas can then be collected and used in down-stream processes. Due to electroconductive material 26 deposited on the surface of mixed phase titanium dioxide particles 16, excited electrons 18 are more likely to be used to split water before recombining with holes 24 than would otherwise be the case. While electrically conductive material 26 is shown deposited on the outside surface of titanium dioxide particle 16, some of the electrically conductive material may reside in the pore structure of the titanium dioxide particles. Notably, system 20 does not require the use of an external bias or voltage source. Further, the efficiency of system 20 allows for one to avoid or use minimal amounts of a sacrificial agent.

[0054] In addition to being capable of catalyzing water splitting without an external bias or voltage, the photocatalysts of the present invention may be included in an anode of an electrochemical cell capable of forming oxygen and hydrogen by electrolysis of water. In a non-limiting example, light energy may be provided to a photocell and from the light energy a voltage between the anode and the cathode is produced and water molecules are split to form hydrogen and oxygen. The method can be practiced such that the hydrogen production rate from water can be modified as desired by subjecting the system to various amounts of light or light flux.

EXAMPLES

[0055] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Example 1

Photocatalyst Preparation

[0056] Synthesis of mixed phase TiO.sub.2 nanoparticle samples A-E. Single phase titanium dioxide anatase nanopowder was commercially purchased (Sigma Aldrich). The nanopowder had a surface area of about 55 m.sup.2/g.sub.catalyst and a particle size of about 20 nm. The nanopowder was annealed isochronally for 1 hour at different temperatures in the range of 700 C. to 800 C. to obtain mixed phase TiO.sub.2 nanoparticle samples A-E. The temperatures and amounts of rutile phase in the samples are listed in Table 1. Table 1 also lists the surface area and particle size of the anatase phase and the rutile phase in the samples. The amount of rutile phase was determined using XRD as described above. The particle size was determined using the Scherrer equation based on the main diffraction line.

[0057] Synthesis of mixed phase TiO.sub.2 microparticle comparison samples F-L. Single phase titanium dioxide anatase micropowder was commercially purchased (Fisher Scientific). The micropowder had a surface area of about 10 m.sup.2/g.sub.catalyst and a particle size of about 100 nm. The micropowder was annealed isothermally at 1000 C. from 1 to 10 hours to obtain mixed phase TiO.sub.2 microparticle samples F-L. The temperature and amounts of rutile phase in the samples is listed in Table 1. Table 1 also lists the surface area and the rutile phase in microparticle samples F-L. The amount of rutile phase was determined using XRD as described above.

[0058] Deposition of Pt on mixed phase TiO.sub.2 materials. The mixed phase TiO.sub.2 nanoparticles and mixed phase TiO.sub.2 microparticles were impregnated with platinum. The platinum precursor solution was prepared by dissolving a calculated amount of platinum chloride (PtCl.sub.2) in 1 normal hydrogen chloride. The calculated amount of precursor solution was then contacted with each of samples A-L. The impregnated mixtures were subjected to stirring and were left at 70-80 C. overnight. The resulting slurries were then dried at 100 C. for 24 hours, followed by calcination at 350 C. for 5 hours in air. The resulting nanoparticle photocatalysts (photocatalysts A-E) and microparticle comparison photocatalysts (photocatalysts F-L) had an elemental platinum content of 1 wt. % based on the total weight of the catalyst.

TABLE-US-00001 TABLE 1 Tem- perature BET d (anatase) d (rutile) Sample ( C.) % Rutile (m2/g) nm nm TiO.sub.2 Anatase 0 55 22 0 (nanoparticles) A 720 3 30 32 8 B 740 10 20 38 38 C 760 29 15 40 76 D 780 37 13.5 45 87 E 800 56 11 48 97 TiO.sub.2 Anatase Microparticles F 1000 0 10 not 0 determined G 1000 0.5 9.8 93 H 1000 1.2 5.4 97 108 I 1000 7.6 5.2 103 114 J 1000 25 6 95 101 K 1000 68 4.5 100 118 L 1000 78 4.5 110 122

[0059] Characterization of Photocatalysts: Characterization of the produced photocatalysts was performed with BET surface areas determination, X-Ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, and transmission electron microscopy.

[0060] X-Ray Diffraction (XRD): Powder XRD patterns of samples A-L were recorded on a Philips Xpert-MPD X-ray powder diffractometer. A 2 interval between 10 and 90 was used with a step size of 0.10 and a step time of 0.5 seconds. The X-ray was a Ni-filtered Cu K radiation source (K=1.5418 ), operated at 45 mA and 40 KV. The percentages of rutile were calculated using Equation (1) above and listed in Table 1. The anatase to rutile ratio was calculated by taking the intensity of anatase phase (101) peak at 2 =25.30 and rutile phase (110) peak at 2 =27.40. Peak positions of anatase (101) and rutile (110) for nanoparticles A-E were shifted with increasing annealing temperature. Peak shifts of 0.3 degrees were observed in 2 values of anatase (101) and rutile (110) from 720 C. to 780 C. A reduction in lattice constants a (0.047 ) and c (0.13.1 ) was observed with an increase in annealing temperature from 720 C. to 780 C. (crystallite size of 45 nm). Peak positions of anatase (101) and rutile (110) for microparticles F-L were in agreement with reported values except for samples I and L, which had a shift in the peaks at lower 2 angles. FIG. 4 is a graphical depiction of photocatalysts A-E of the transformation of the anatase phase to the rutile phase when an anatase nanoparticle powder is heated between 720 C. and 780 C. for one hour. In FIG. 4, the anatase phase (101) peak is at 2 theta=25.5 degree and the rutile phase (110) peak is at 2 theta=27.7 degrees. Data (a) represents heating single phase TiO2 anatase at 720 C. for one hour. Data (b) represents heating the single phase TiO.sub.2 anatase at 740 C. Data (c) represents heating the single phase TiO.sub.2 anatase at 760 C. Data (d) represents heating the single phase TiO.sub.2 anatase at 780 C. Data (e) represents heating the single phase TiO.sub.2 anatase at 80 C. FIG. 5 are XRD spectra of microparticle comparison photocatalysts F-L. The metals are not seen by XRD due to their concentrations being too weak to detect.

[0061] UV Absorption: UV-Vis absorbance spectra of the powdered catalysts were collected over the wavelength range of 250-900 nm on a Thermo Fisher Scientific UV-Vis spectrophotometer equipped with praying mantis diffuse reflectance. Samples were grounded using mortar and pestle before being introduced into the praying mantis chamber using a sample cup. Reflectance (% R) of the samples was measured. A 100 Watt ultraviolet lamp (H-144GC-100, Sylvania par 38) was used as a UV source with a flux of up to 3 mW/cm.sup.2, depending on the distance from the source, with the cut off filter (360 nm and above). The Kubelka-Munk function, F(R)=(1R).sup.2/(2R), was used to calculate the optical absorbance from the reflectance (R) of the samples compared to the standard. Band gap was estimated from the Tauc plot of the quantity (F(R) E).sup.1/2 against the radiation energy. FIG. 6 depicts UV-Vis spectra of absorbance in Tauc units versus electron volts (eV) of 1 wt. % Pt/TiO.sub.2 nanoparticle photocatalysts A-E with different percentages of rutile. Data line 602 is 0% rutile, data line 604 is 3% rutile, data line 606 is 10% rutile, data line 608 is 29% rutile, and data line 610 is 37% rutile. The dotted lines are the slope of each of the respective lines. FIG. 7 depicts a UV-Vis spectrum of absorbance in Tauc units versus electron volts (eV) of 1 wt. % Pt/TiO.sub.2 microparticle comparison photocatalysts F-L with different percentages of rutile. The rise above 3.0 eV is due to the absorption of TiO.sub.2. Data line 702 is 0.5% rutile, data line 704 is 1.2% rutile, data line 706 is 7.6% rutile, data line 708 is 25% rutile, data line 710 is 68% rutile, and data line 712 is 78% rutile. As shown in FIG. 6, the pure anatase has a band gap of 3.2 eV and with the increase in rutile content the band gap decreases up to 3.0 eV with the maximum rutile content of 37%. As shown in FIG. 7, the decrease in band gap up to 3.0 eV for the microparticle photocatalyst was observed with an increase in rutile content, however, the rutile content was 78%.

[0062] Based on the observed band gap data, one would expect that the comparison photocatalysts containing mixed phase TiO.sub.2 microparticles having up to 78% rutile and the photocatalyst of the invention having mixed phase TiO.sub.2 nanoparticles having up to 38% rutile would have similar hydrogen production rates in a water-splitting process.

[0063] X-Ray Photoelectron Spectroscopy (XPS): XPS was conducted using a Thermo scientific ESCALB 250 Xi. The base pressure of the chamber ranged from 10-10 to 10-11 mbar. Charge neutralization was used for all samples. Spectra were calibrated with respect to C1s at 285.0 eV, Pt4f, O1s, Ti2p, C1s, and valence band energy regions were scanned for all materials. Typical acquisition conditions were as follows: pass energy=30 e V and scan rate=0.1 e V per 200 ms. Argon ion bombardment was performed with an EX06 ion gun at 1 kV beam energy and 10 rnA emission current; sample current was typically 0.9-1.0 nA. Self-supported oxide disks of approximately 0.5 cm diameter were loaded into the chamber for analysis.

[0064] FIG. 8 are XPS spectra of the Pt4f of 1 wt. % Pt/TiO.sub.2 microparticle photocatalysts F-L. The chemical compositions of Pt on the surface, the ratios of Pt4f/Ti2p and O1s/Ti2p were calculated using the corrected area under the XPS curves of Pt4f.sub.7/2 and Pt4f.sub.5/2 and are listed in Table 2. Platinum was mostly present in the oxidized form in all samples (Pt.sup.2+). The peaks at 72.6-72.8 eV were assigned to Pt4f.sub.7/2 of Pt.sup.2+ while the peaks at 75.9- 76.1 eV were assigned to Pt4f.sub.5/2 of Pt.sup.2+. The peak positions at 71.5 eV were related to Pt4f.sub.7/2 of metallic Pt peak, while peaks at 74.8 eV were attributed to Pt4f.sub.5/2 of Pt.sup.0. The metallic percentage of Pt was more pronounced in the sample containing 100% anatase.

TABLE-US-00002 TABLE 2 % Rutile Atomic % Pt4f/Ti2P O1s/Ti2P 0.5 Pt4f 1.1 0.05 Ti2P 24.2 O1s 53.3 C1s 21.3 1.2 Pt4f 1.6 0.07 Ti2P 23.5 O1s 52.4 C1s 22.3 7.6 Pt4f 1.1 0.05 Ti2P 23.4 O1s 52.8 C1s 22.5 25 Pt4f 1.2 0.05 Ti2P 22.5 O1s 52.4 C1s 23.5 68 Pt4f 0.9 0.04 Ti2P 24.1 O1s 56.1 C1s 18.9 78 Pt4f 1.9 0.04 2.3 Ti2P 23.7 O1s 55.1 C1s 20.2

[0065] FIG. 9 are XPS spectra of the Pt4f of photocatalyst B having 1 wt. % Pt/TiO.sub.2 nanoparticles having 10% rutile and comparison photocatalyst having 1 wt. % Pt/TiO.sub.2 anatase (100%). XPS analysis was carried out for these samples before and after Ar ion sputtering. The oxidation states of Pt in the non-Ar sputtered samples are attributed to Pt.sup.2+ and Pt.sup.4+. The peaks at 72.7 and 76.0 eV are attributed to Pt4f.sub.7/2 and Pt4f.sub.5/2 of Pt.sup.2+ while peaks at 75.0 and 78.2 eV corresponded to Pt4f.sub.7/2 and Pt4f.sub.5/2 of Pt.sup.2+. After Ar ion sputtering for 5 minutes, the nanoparticle sample was reduced and the oxidation states of Pt changed to metallic platinum; peaks positions shifted to the lower binding energy at 71.7 and 75.0 for Pt4f.sub.7/2 and Pt4f.sub.5/2 of Pt.sup.0 with the difference in the splitting binding energies of 3.3 eV.

[0066] Based on the data obtained from XPS, the photocatalysts of the invention have a band gap between about 3.0 eV and 3.2 eV.

[0067] FIG. 10 are XPS spectra of the Ti2p of pure rutile, pure anatase, and the mixed phase microparticles (78% rutile, comparison sample L). The spectra were aligned to the C1s at 285.0 eV. The Ti2p of rutile is found to be about 0.2 eV lower in binding energy compared to that of anatase. The narrow full width half maximum (FWHM) of all the samples indicated that no contribution of reduced states was present. It should be noted that the FWHM of the Ti2p.sub.3/2 of the mixed phase sample is larger than that of FWHM of the Ti2p.sub.3/2 the samples containing rutile alone or anatase alone. FIGS. 11 and 12 depict the XPS of the Valence Band region of pure 1 wt. % Pt/TiO.sub.2 rutile, 1 wt. % Pt/TiO.sub.2 anatase, and 1 wt. % Pt/TiO.sub.2 mixed phase after AR ions sputtering. The spectra are aligned to the O2s binding energy and the base line is shifted so all spectra have the same initial offset for better comparison. The alignment to the O2s prevented the effect of any possible nonlinearity in the spectrometer because the C1s region is relatively far (260 eV above the O2p region). Non-Ar sputtered material was compared to that of the sputtered material to see into any effect due to the presence of Ti3d states associated with oxygen defects. In FIG. 11, the rutile VB with its finger print of the O2p shape was evident. Ar ion sputtering resulted in the appearance of lines extending from about 1 eV below the Fermi level (shaded area). As shown in FIG. 11, the mixed phase TiO.sub.2 has the O2p shape dominated by that of anatase. FIG. 12 depicts similar spectra as FIG. 11, but starting from pure anatase. Inspection of both figures indicate that the VBM of anatase is at a lower energy than that of rutile and that the mixed phase materials is somewhere in between. Based on FIGS. 11 and 12, the VBM of the mixed phase material falls in between that of anatase and that of rutile.

Example 2

Use of Photocatalysts in Water-Splitting Reactions

[0068] Experimental Set-Up: Catalytic reactions were conducted in a borosilicate (Pyrex, Corning) glass reactor having a capacity of 100 mL. For each experiment, a photocatalyst was added to the glass reactor in a concentration of 0.1 g/L (25 mg in 21 mL total volume). The photocatalyst was reduced under hydrogen flow at 350 C. for 1 h followed by purging with nitrogen gas for 30 minutes. Deionized water (20 mL) and sacrificial agent (ethanol, 5 v/v % based on total water, 1 mL) were added to the reactor. The reaction mixture was irradiated with sunlight, with a light flux at the front side of the reactor of between 0.3 and 1 mW/cm.sup.2. The mixture containing photocatalyst, water and sacrificial agent was stirred constantly under dark conditions to disperse the catalyst and sacrificial agent in the water. The reactor was then exposed to a UV light source (100 Watt UV lamp (H-144GC-100, Sylvania par 38) with a flux of about 2 mW/cm.sup.2 at a distance of 10 cm with the cut off filter (360 nm and above). Product analysis of the produced gas was done using a gas chromatography (Porapak Q (Sigma Aldrich) packed column 2 m, 45 C. (isothermal), with nitrogen as a carrier gas) with a thermal conductivity detector. Hydrogen production rates for reactions run with photocatalysts A-L were normalized with respect to BET surface area of each catalyst. FIGS. 13, 14, and 15 are graphical depictions of hydrogen production in mol/m.sup.2.sub.cat versus time in minutes for nanoparticles and microparticles of 1 wt. % Pt/TiO.sub.2. FIG. 13 is a graphical depiction of hydrogen production versus time for 1 wt. % Pt/TiO.sub.2 nanoparticles with increasing rutile content. FIG. 14 is a graphical depiction of hydrogen production versus time for 1 wt. % Pt/TiO.sub.2 microparticles with increasing rutile content. FIG. 15 is a graphical depiction of hydrogen production from 1 wt. % Pt/TiO.sub.2 nanoparticles and 1 wt. % Pt/TiO.sub.2 microparticles versus rutile content.

[0069] As shown in FIGS. 13-15, 1 wt. % Pt/TiO.sub.2 100% rutile (pure rutile) produced the least amount of hydrogen, namely 2.610.sup.8 mol/m.sup.2 per min for the nanoparticles and 5.310.sup.8 mol/m.sup.2 per min for the microparticles. The rate of hydrogen production using 1 wt. % Pt/TiO.sub.2 100% anatase was 110.sup.6 mol/m.sup.2 per min for nanoparticles and about 2.410.sup.6 mol/m.sup.2 per min for microparticles, which is about 2 orders of magnitude higher than 1 wt. % Pt/TiO.sub.2 100% rutile. The rate of hydrogen product for the mixed phase photocatalyst containing 1 wt. % Pt/TiO.sub.2 microparticles decreased as the increase in the amount of rutile in the titanium dioxide increased. Thus, one would predict that hydrogen production from a mixed phase photocatalyst containing 1 wt. % Pt/TiO.sub.2 nanoparticles would decrease over time with increasing amounts of rutile phase in the titanium dioxide and be less than the amount of hydrogen produced using the mixed phase titanium dioxide nanoparticles. It was found, however, that when the photocatalysts containing mixed phase titanium dioxide nanoparticles having a ratio of anatase to rutile of at least 1.5 were used, the production of hydrogen was greater than (See, for example, FIG. 15) that of the comparison photocatalyst containing mixed phase titanium dioxide microparticles having a substantially same amount of anatase and rutile phases as the titanium dioxide nanoparticles under the same conditions.