Oxidation catalysts on alkaline earth supports

Abstract

An oxidation catalyst includes a support including particles of an alkaline earth salt, and first particles including a palladium compound on the support. The oxidation catalyst can also include precious metal group (PMG) metal particles in addition to the first particles intermixed together on the support. A gas permeable polymer that provides a continuous phase can completely encapsulate the particles and the support. The oxidation catalyst may be used as a gas sensor, where the first particles are chemochromic particles.

Claims

1. An oxidation catalyst, comprising: a support comprising particles of an alkaline earth salt, and first particles comprising at least a palladium compound on said support, and a gas permeable polymer that provides a continuous phase that completely encapsulates said first particles and said support.

2. The oxidation catalyst of claim 1, wherein said alkaline earth salt comprises a sulfate, a carbonate, a hydroxide, an oxide, or a sulfide.

3. The oxidation catalyst of claim 1, wherein said alkaline earth salt comprises BaSO.sub.4.

4. The oxidation catalyst of claim 1, wherein said palladium compound comprises palladium oxide, palladium hydroxide, or a palladium salt.

5. The oxidation catalyst of claim 1, wherein said first particles further comprise precious metal group (PMG) metal particles intermixed with particles of said palladium compound on said support.

6. The oxidation catalyst of claim 5, wherein said PMG metal particles comprise at least one of gold, silver and a platinum group metal.

7. The oxidation catalyst of claim 1, further comprising an ultraviolet (UV) absorber or UV blocker, or a mixture thereof on said support.

8. The oxidation catalyst of claim 7, wherein said UV blocker comprises zinc oxide or titania.

9. The oxidation catalyst of claim 7, wherein said UV absorber comprises a triazine compound, a benzophenone, or a benzotriazol.

10. The oxidation catalyst of claim 1, wherein said gas permeable polymer comprises silicone rubber or silicone resin.

11. An oxidation catalyst, comprising: a support comprising BaSO.sub.4 particles, and first particles comprising PdO particles said support, and a gas permeable polymer that provides a continuous phase that completely encapsulates said first particles and said support.

12. The oxidation catalyst of claim 11, further comprising precious metal group (PMG) metal particles intermixed with said PdO particles on said support.

13. A method of forming an oxidation catalyst, comprising: providing a support comprising a plurality of particles of an alkaline earth salt depositing first particles comprising a palladium compound on said support while in a liquid phase including at least one solvent; removing said liquid phase to provide said oxidation catalyst, and forming a gas permeable polymer that provides a continuous phase that completely encapsulates said first particles and said support.

14. The method of claim 13, wherein said liquid phase is a slurry including said plurality of particles of said alkaline earth salt in said solvent, and said removing said liquid phase includes baking and then sonication after said baking.

15. The method of claim 13, wherein said alkaline earth salt comprises BaSO.sub.4.

16. The method of claim 13, wherein said depositing said first particles comprises co-depositing said first particles together with precious metal group (PMG) metal particles to form mixed metal comprising particles.

17. The method of claim 16, wherein said PMG metal particles comprise at least one of gold, silver and a platinum group metal.

18. The method of claim 13, wherein said solvent comprises an alcohol and said depositing comprises sonication.

19. The method of claim 13, wherein said forming gas permeable polymer comprises: admixing a moisture or heat curable silicone sealant with said plurality of particles of said alkaline earth salt and said first particles, and curing said silicone sealant to form a rubbery gas permeable silicone polymer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1A is a cross sectional depiction of an example oxidation catalyst comprising a support including particles of an alkaline earth metal salt and first particles comprising a palladium compound on the support, according to an example embodiment.

(2) FIG. 1B is a cross sectional depiction of an example oxidation catalyst comprising a support comprising particles of an alkaline earth metal salt, and mixed particles on the support including first particles comprising a palladium compound and second particles comprising a PMG metal, according to an example embodiment.

(3) FIG. 1C is a cross sectional depiction of an example encapsulated oxidation catalyst comprising the oxidation catalyst in FIG. 1B along with an optional reducing gas permeable polymer that forms a continuous phase which provides complete encapsulation for the alkaline earth salt support particles and the and mixed particles, according to an example embodiment.

(4) FIG. 2 shows E vs. exposure time to 100% H.sub.2 gas sensing performance for various disclosed platinum-doped Pd/TiO.sub.2 supported oxidation catalysts used as pigments encapsulated in DOW 734 silicone resin that were synthesized as compared to a known PdO on TiO.sub.2 control (no Pt doping).

(5) FIG. 3 shows E vs. exposure time to 100% H.sub.2 sensing gas for various disclosed PdO/BaSO.sub.4 oxidation catalysts (BaSO.sub.4 as supports) used as pigments encapsulated in DOW 734 silicone resin that were synthesized as compared to a known (base) PdO on TiO.sub.2 oxidation catalyst control (no Pt doping).

(6) FIG. 4 shows E vs. exposure time to 100% H.sub.2 sensing gas for disclosed embodiments including platinated BaSO.sub.4, large scale batch barium sulfate that was baked before sonication, and large scale batch barium sulfate that was sonicated before being baked, according to example embodiments.

(7) FIG. 5 shows E vs. exposure time to 100% H.sub.2 sensing gas for disclosed gas permeable polymer encapsulated BaSO.sub.4 supported PdO chemochromic pigment samples which demonstrates excellent E vs. time performance for both the clear and clear/white polymer embodiments.

DETAILED DESCRIPTION

(8) Disclosed embodiments in this Disclosure are described with reference to the attached figures, wherein like reference numerals are used throughout the figures to designate similar or equivalent elements. FIGS. 1A-C are not drawn to scale, and they are provided merely for illustration. Several aspects are described below with reference to example applications for illustration.

(9) It should be understood that numerous specific details, relationships, and methods are set forth to provide a full understanding of the disclosed embodiments. One having ordinary skill in the relevant art, however, will readily recognize that the subject matter disclosed herein can be practiced without one or more of the specific details or with other methods. In other instances, well-known structures or operations are not shown in detail to avoid obscuring structures or operations that are not well-known. This Disclosure is not limited by the illustrated ordering of acts or events, as some acts may occur in different orders and/or concurrently with other acts or events. Furthermore, not all illustrated acts or events are required to implement a methodology in accordance with this Disclosure.

(10) Notwithstanding that the numerical ranges and parameters setting forth the broad scope of this Disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein. For example, a range of less than 10 can include any and all sub-ranges between (and including) the minimum value of zero and the maximum value of 10, that is, any and all sub-ranges having a minimum value of equal to or greater than zero and a maximum value of equal to or less than 10, e.g., 1 to 5.

(11) Disclosed embodiments include alkaline earth metal salt particle supports which provide significantly improved catalyst performance including kinetics and detection sensitivity over conventional titania supports. One example alkaline earth support is a BaSO.sub.4 support. However, the alkaline earth support material can generally include all other alkaline earth elements (Be, Mg, Ca, Sr, or Ra), and can be in forms other than sulfate, such as carbonate, hydroxide, oxide, or sulfide.

(12) Some disclosed embodiments are based on the discovery that a palladium compound oxidation catalyst such as PdO on a support when doped with particles comprising a PMG metal provides supported oxidation catalysts which oxidize a reducing gas (e.g., hydrogen, carbon monoxide, or hydrocarbons) with oxidation kinetics sped up significantly and sensitivity increased significantly as compared to the palladium compound (e.g., PdO) on the support alone. Disclosed alkaline earth metal salt particle supports (e.g., BaSO.sub.4) may be combined with doping of the palladium compound (e.g., PdO) with a PMG metal, which as evidenced in the Examples below may further improve oxidation kinetics and detection sensitivity of the oxidation catalyst.

(13) In the doped embodiments, the PMG metal particles feature the metal being in its atomic/elemental form which may be clearly contrasted with metal in metal compounds, such as compounds selected from the group consisting of oxides, hydroxides and hydrated oxides of platinum group metals. As well known in metallurgy, physics and chemistry, an elemental (or atomic) metal is in its elemental uncharged state while metals in metal compounds are in an ionic (generally cationic) state. For example, for the conventional PdO pigment, Pd is in the +2 state (Pd.sup.+2), and as known in the art, and upon exposure to a reducing gas such as H.sub.2, Pd.sup.+2 reduces to its elemental/atomic form Pd.sup.0 which results in a visible color change (and the generation of water). An elemental metal such as Pd.sup.0 cannot itself accept electrons.

(14) The support is generally selected so that interaction of the metal particles with the surface of support surfaces minimizing the total energy required for palladium compound (e.g., PdO) reduction. This suggests a small chemical interaction between support and the metal particles and hence destabilization of the palladium compound particles on the surface of the support, such as the PMG metal dopant (e.g. Pt) lowering the activation energy required for PdO reduction.

(15) Disclosed supported oxidation catalysts embodied as chemochromic sensors (pigments) change color in a presence of at least one reducing gas. Embodied as chemochromic reducing gas sensors, disclosed reducing gas sensors are irreversible sensors.

(16) The response time of disclosed chemochromic reducing gas sensors toward H.sub.2 gas by including nanosized PMG dopant particles with palladium compound particles (e.g., PdO) has been found to unexpectedly be decreased by about 10 fold while encapsulated in a silicone resin. As noted above, disclosed supported oxidation catalysts can also be used as catalysts, such as to reduce undesirable emissions from fossil fuel powered vehicles. Moreover, as also noted above, use of disclosed alkaline earth metal salt particle supports provide further improvement in catalyst or reducing gas function including both kinetics and detection sensitivity.

(17) FIG. 1A is a cross sectional depiction of an example oxidation catalyst 100 comprising a support 101 comprising particles of an alkaline earth metal salt, and at least first particles 102 being particles comprising a palladium compound on the support 101, according to an example embodiment. For gas detection applications, the first particles 102 comprise chemochromic particles.

(18) Although the support 101 is shown in FIG. 1A in layer form, such as comprising a polycrystalline layer, the support 101 may also be in discrete particle form. Typically the support 101 comprises alkaline earth metal salt particles which are generally colorless, white, or slightly colored.

(19) In one embodiment, the support 101 comprises alkaline earth metal salt particles having a size in a range from 0.1 m to 1.0 m, and in one particular embodiment from 0.2 m to 0.25 m for pigment applications to maximize opacity.

(20) The first particles 102 can comprise palladium oxide, palladium hydroxide, or a palladium salt. The first particles 102 can have a median size in the range of 2 nm to 8 nm.

(21) In typical applications, the supported oxidation catalyst 100 can be adhered to a substrate where it can provide its chemochromic reducing gas sensing or catalyst function, such as on a metal surface (e.g. a metal wall). The shapes of the support 101, first particles 102 and optional second particles 103 shown in FIGS. 1B and 1C are arbitrary.

(22) FIG. 1B is a cross sectional depiction of an example supported oxidation catalyst 130 comprising a support 101 comprising particles of an alkaline earth metal salt, first particles 102 comprising a palladium compound (e.g., PdO), and optional second particles 103 comprising a PMG metal, on the support 101, according to an example embodiment. Disclosed PMG's can include gold, silver, or platinum group metals, such as ruthenium, rhodium, osmium, iridium, and platinum.

(23) In one embodiment the second particles 103 have a median size in the range from 5 nm to 10 nm. The relative concentration ratio of the second particles 103 to first particles 102 can range from 1:10 to 1:25 by weight.

(24) Disclosed supported oxidation catalysts can further comprise an ultraviolet (UV) absorber or UV Blocker, or a mixture thereof to remedy possible adverse environmental effects. The UV blocker can comprise ZnO.sub.2 or TiO.sub.2. The UV absorber can comprise compounds from the triazine family, such as benzotriazol or a benzopheneone. The UV absorber or UV Blocker can be in the range of 1-10 wt. % of the supported oxidation catalyst. Although not shown in FIGS. 1A-C, UV absorber or UV Blocker particles if shown would be on the support 101 analogous to first particles 102 or second particles 103 (FIG. 1B), or can be physically mixed with the oxidation catalyst.

(25) FIG. 1C is a depiction of an example encapsulated supported oxidation catalyst 150, according to an example embodiment. Encapsulated supported oxidation catalyst 150 comprises the oxidation catalyst 130 comprising a support 101 including the alkaline earth metal salt particles shown in FIG. 1B along with an optional reducing gas permeable polymer 104 that forms a continuous phase (matrix) which provides complete encapsulation for the alkaline earth metal salt particles and mixed particles comprising first particles 102 and optional second (PGM metal) particles 103.

(26) The gas permeable polymer 104 continuous phase can be formed by admixing a suitable material, such as a moisture curable or heat curable silicone sealant with dry catalyst particles or its slurry comprising alkaline earth metal salt particles which will be the support 101, first particles (palladium compound) 102, and optional second particles of PMG metal 103 in a liquid phase before drying. Upon curing the silicone sealant a rubbery gas permeable silicone polymer forms a continuous phase that provides complete encapsulation as shown in FIG. 1C.

(27) In some embodiments, the supported oxidation catalyst can comprise a composite layer. A composite layer is known in the material arts and is defined herein as a composite engineered material made from two or more constituent materials with significantly different physical or chemical properties which remain separate and distinct on a macroscopic level within the finished structure. In principle, composites can be constructed of any combination of two or more materials, metallic, organic, or inorganic; but the constituent forms are typically more restricted. The matrix provided by the gas permeable polymer 104 is the body constituent, acting as a continuous phase having the other materials referred to as the additive phases embedded therein, with the gas permeable polymer 104 serving to enclose the other composite components and give it bulk form.

(28) Disclosed embodiments also include methods of forming disclosed oxidation catalysts. A support is provided, such as comprising a plurality of alkaline earth metal salt particle particles. First particles comprising a palladium compound (e.g., PdO) and optionally second particles comprising a PMG metal are deposited on the alkaline earth metal salt particle support(s) in a liquid phase slurry including a solvent to form nanosized palladium compound (e.g., PdO) particles and PMG metal particles. A solid-liquid separation process such as filtering the slurry allows removal of the liquid phase to form dried solid supported oxidation catalyst which may be referred to as composite particles.

(29) The depositing can comprise co-depositing the first particles comprising the palladium compound and the optional PMG metal particles using a precursor for the palladium compound and a precursor for the PMG metal. As described below, depositing the palladium compound after depositing the PMG metal under reflux condition may provide enhanced sensing performance.

(30) In one embodiment for gas sensing or detection, the method further comprises admixing a moisture curable silicone sealant with the particles in the liquid phase, and then curing the moisture curable silicone sealant to form a rubbery gas permeable silicone polymer. In this embodiment, the gas permeable polymer provides a continuous phase that completely encapsulates the first particles comprising the palladium compound, the second particles comprising the PMG metal, and the alkaline earth metal salt particle supports (see FIG. 1C described above).

(31) As noted above, disclosed supported oxidation catalysts can be used in a variety of applications including in the development of chemochromic passive sensors for detecting reducing gases such as hydrogen, carbon monoxide, and hydrocarbons (e.g., natural gas or propane). These gases/liquids are widely used and produced in many industries and a safe operation is a top priority for all of them. Disclosed alkaline earth metal salt particle supported oxidation catalysts can also provide a layer of protection against accidental releases of these gases and therefore reinforces a safe manufacturing/utilization environment. Furthermore, disclosed supported oxidation catalysts can be used as catalysts in the automotive industry to reduce hydrocarbon, carbon monoxide, and NOx emissions, or in any industry that carry methane combustion such as natural gas-powered vehicles. Other example applications include depollution of natural gas-powered vehicles, and catalytic processes for energy production from natural gas.

(32) The effectiveness of gas sensors, such as disclosed supported oxidation catalysts used as chemochromic reducing gas sensors, is typically evaluated by measuring the time necessary to reach a given level of color change, and by determining the total amount of color change. The latter is expressed as E and is measured by a colorimeter. E measures a difference in color by measuring specific parameters of the film (L, a, b). These parameters refer to a color system for measuring absolute chromaticity, L*a*b* and color difference (L*a*b*) or E. Color is defined in three dimensions: hue, chroma (saturation) and lightness. L*=the gradient from light to dark, a*=the gradient from red to green, and b*=the gradient from yellow to blue, and E*={(L*).sup.2+(a*).sup.2+(b*).sup.2}.sup.1/2. This equation gives a standard measurement technique by which one can compare color changes from different chemochromic reducing gas sensor film samples. The greater the E* value, the greater the color contrast. Chemochromic reducing gas sensor films can be analyzed both before and after exposure to the reducing gas, allowing quantification of the intensity of the color change.

EXAMPLES

(33) Disclosed embodiments are further illustrated by the following specific Examples, which should not be construed as limiting the scope or content of this Disclosure in any way. For example, although the alkaline earth supports are described in the Examples as being BaSO.sub.4 supports, alkaline earth supports can generally include all other alkaline earth elements and be in forms other than sulfate, such as carbonate, hydroxide, oxide, or sulfide. Moreover, as noted above, although Pt is generally used as the dopant in these examples, Pt can be replaced by gold, silver, or another PGM other than Pt.

(34) Example methods of preparation of disclosed supported oxidation catalysts are now described. Samples referred to as base in FIGS. 2-3 such as PK-1-135 NM1 and PK-2-50-NM1-1 respectively, described below refer to known PdO on TiO.sub.2 support controls (no Pt doping). For testing, the samples were all placed inside a vial and were exposed to 100% H.sub.2 gas with a 45 ml/min flow rate. The Examples are all based on 10 g batches of support (TiO.sub.2 or BaSO.sub.4) except for the large scale batches of support which were 250 g batches.

Example 1

Depositing 0.3 Wt. % PT Doping onto PdO/TiO2 by Reflux

Example 1A

(35) To deposit PdO particles on TiO.sub.2 (titania), a slurry of .sub.2.5 g TiO.sub.2 in 100 mL water was adjusted to pH 10.6 using 12 M NaOH and stirred at 70 C. for an hour. 2.5 mL of 0.281M PdCl.sub.2 solution in 2 M HCl was added dropwise to the mixture, taking care to keep the solution at pH 10.6 using 12 M NaOH. Once all the PdCl.sub.2 solution was added, the pH of the mixture was adjusted to 8 using 3 M HCl. This mixture was stirred and heated for an hour while the PdO was deposited onto surfaces of the titania. The resulting PdO/TiO.sub.2 solid product was then filtered, washed thoroughly with water, and dried under vacuum at 200 C. for 3 hours. The PdO/TiO.sub.2 solid product was used to provide the PK-1-135 NM1 controls.

Example 1B

(36) 0.019 g Na.sub.2PtCl.sub.6 was added to a slurry of 2.5 g PdO/TiO.sub.2 in 100 mL DI water. 0.027 g sodium citrate was added to the mixture, which was then placed under reflux at 70 C. and stirred overnight (16 hours). The Pt on PdO/TiO.sub.2 solid product was filtered, washed thoroughly with water and dried under vacuum at room temperature to provide a disclosed supported oxidation catalysts identified as PK-1-136-NM13.

(37) FIG. 2 which shows E vs. exposure time to 100% H.sub.2 gas for various disclosed Pt doped PdO/TiO.sub.2 supported oxidation catalysts used as pigments encapsulated in DOW 734 silicone resin, along with PK-1-135 NM1 (Base) for a PdO on TiO.sub.2 control. The performance of PK-1-136-NM13 can be seen to be similar to PK-1-135 NM1.

(38) PK-1-137-NM15 was prepared by reversing the order of steps 1A and 1B. First Pt was deposited onto a TiO.sub.2 support (Step 1B) and then PdO was deposited onto Pt/TiO.sub.2 by following step 1A (its E vs. exposure time to 100% H.sub.2 gas is shown in FIG. 2). PK-1-137-NM15 can be seen to provide a significant performance enhancement compared to the PK-1-135 NM1 base control and PK-1-136-NM13.

Example 2

Depositing 0.3 Wt % Pt onto a PdO/TiO2 Support by Sonication

Example 2A

(39) To deposit PdO, a slurry of 2.5 g TiO.sub.2 in 100 mL water was adjusted to pH 10.6 using 12 M NaOH and stirred at 70 C. for an hour. 2.5 mL of 0.281M PdCl.sub.2 solution in 2 M HCl was added dropwise to the mixture, taking care to keep the solution at pH 10.6 using 12 M NaOH. Once all the PdCl.sub.2 solution was added, the pH of the mixture was adjusted to 8 using 3 M HCl. This mixture was stirred and heated for an hour while the PdO was deposited onto surfaces of the titania. The solid PdO/TiO.sub.2 product was filtered, washed thoroughly with water and dried at room temperature.

Example 2B

(40) Then, 0.019 g Na.sub.2PtCl.sub.6 was added to a slurry of 2.5 g PdO/TiO.sub.2 in 100 mL ethanol to give a loading of 0.3 wt % Pt on the support. The pH of the solution was adjusted to 6 using 12 M NaOH. Sonication was carried out on the reaction mixture using a direct immersion titanium tip (20 kHz, 100 W cm.sup.2) at room temperature. Sonication uses applied sound energy to agitate particles in the sample. The resulting solid Pt on PdO/TiO.sub.2 product was filtered, thoroughly washed with ethanol, dried at room temperature and then baked at 200 C. for 3 hrs to provide PK-1-135-NM-20 (its E vs. exposure time to 100% H.sub.2 gas is shown in FIG. 2). PK-1-135-NM-20 can be seen to provide a significant performance enhancement compared to the PK-1-135 NM1 base control.

(41) PK-1-142-NM31 was prepared by reversing the order of steps 2A and 2B. First, Pt was deposited onto a TiO.sub.2 support (Step 2B), and then PdO was deposited onto Pt/TiO.sub.2 by following step 2A (its E vs. exposure time to 100% H.sub.2 gas is shown in FIG. 2). PK-1-142-NM31 can also be seen to provide a significant performance enhancement compared to the PK-1-135 NM1 base control.

Example 3

Synthesis of an Irreversible BaSO4/PdO 3 Wt % PdO Chemochromic Pigment (BaSO4 Supports)

(42) A slurry of 2.5 g BaSO.sub.4 in 100 mL water was adjusted to pH 10.6 using 12 M NaOH and stirred at 70 C for an hour. 2.5 mL of 0.281M PdCl.sub.2 solution in 2 M HCl was added dropwise to the mixture, taking care to keep the solution at pH 10.6 using 12 M NaOH. Once all the PdCl.sub.2 solution was added, the pH of the mixture was adjusted to 7 using 3 M HCl. This mixture was stirred and heated for an hour while the PdO was deposited onto the surfaces of the BaSO.sub.4. The solid product was filtered, washed thoroughly with water and dried under vacuum at 110 C. for 3 hours to provide PK-2-124-NM48C-1 (shown in FIG. 3). The catalyst PK-2-142-NM55 (shown in FIG. 3) was synthesized by adding ethanol to PK-1-124-NM48C-1 and sonicating the slurry using a direct immersion titanium tip (20 kHz, 100 W cm.sup.2) at room temperature.

Example 4

Exposure of PdO/BaSO4 Pigments (BaSO4 Supports)

(43) FIG. 3 shows E vs. exposure time performance for two synthesized PdO/BaSO.sub.4 pigments (see PK-2-124-NM48C-1 and PK-2-142-NM55 in FIG. 3) encapsulated in DOW 734 silicone resin. PK-2-142-NM55 can be seen in FIG. 3 to provide a significant performance enhancement compared to the PK-2-50 NM1-1 base titania support control. The PdO/BaSO.sub.4 oxidation catalysts prepared by sonication (30 kHz) showed a response time curve very similar to the disclosed Pt doped PdO/TiO.sub.2 catalyst shown as PK-2-125-NM-20-2. The BaSO.sub.4 supported catalyst thus eliminated the need for the PMG metal dopant, and therefore will be comparatively more cost effective. However, as noted above, BaSO.sub.4 can be used with PMG metal dopants for even faster kinetics.

Example 5

Depositing 0.3 Wt % Pt onto a PdO/BaSO4 Support by Sonication

(44) To deposit PdO, a slurry of 10 g BaSO.sub.4 in 100 mL water was adjusted to pH 10.6 using 2.56 M NaOH and stirred at 70 C. for one hour. 10 mL of 0.28 M PdCl.sub.2 solution in 2 M HCl was added dropwise to the mixture, taking care to keep the solution at pH 10.6 using 2.56 M NaOH. Once all the PdCl.sub.2 solution was added, the pH of the mixture was adjusted to 7 using 2 M HCl. This mixture was stirred and heated for one hour while the PdO was deposited onto the surfaces of the BaSO.sub.4. The solid PdO/BaSO.sub.4 was filtered, washed thoroughly with ethanol, dried at room temperature overnight, and dried at room temperature in a vacuum oven for one hour. Then, 4 mL of 0.02 M Na.sub.2PtCl.sub.6 was added to a slurry of 5 g PdO/BaSO.sub.4 in 100 mL ethanol to give a loading of 0.3 wt % Pt onto the support. Sonication was carried out on the reaction mixture using a direct immersion titanium top (30 kHz, 100 W cm.sup.2) at room temperature. The solid Pt on PdO/BaSO.sub.4 product was filtered, thoroughly washed with ethanol, dried at room temperature overnight, dried at room temperature in a vacuum oven for one hour, and baked at 110 C. for 3 hours to form a disclosed supported oxidation catalyst including Pt doped PdO on a BaSO.sub.4 support.

Example 6

Synthesis of Large Scale Irreversible BaSO4/PdO 3 Wt % PdO Chemochromic Pigment (BaSO4 Supports)

Example 6A

(45) To deposit PdO particles on BaSO.sub.4, a slurry of 250 g BaSO.sub.4 (a large scale batch of supports) in 2000 mL water was adjusted to pH 10.6 using 2.56 M NaOH and stirred at 70 C. for one hour. 250 mL of 0.28 M PdCl.sub.2 in 2 M HCl and 250 mL 2.56 M NaOH was added to the mixture by automated injection, taking care to keep the solution at pH 10.6 using 2.56 M NaOH or 2 M HCl. Once all the PdCl.sub.2 and NaOH was added, the pH of the mixture was adjusted to pH 7 using 2M HCl. This mixture was stirred and heated for one hour while the PdO was deposited onto the surfaces of the BaSO.sub.4. The solid PdO/BaSO.sub.4 product was filtered, washed thoroughly with ethanol, dried at room temperature overnight, and dried at room temperature in a vacuum oven for one hour.

Example 6B

(46) A slurry of the product from Example 6A in 1000 mL ethanol was sonicated using a direct immersion titanium tip (60 kHz, 100 W cm.sup.2) at room temperature. The solid PdO/BaSO.sub.4 product was filtered, thoroughly washed with ethanol, dried at room temperature overnight, and dried in a vacuum oven at room temperature for one hour. The product was then baked at 110 C. for 3 hours. The large scale batch produced evidences the scalability of the disclosed barium sulfate supported pigment.

Example 6C

(47) The product from Example 6A was baked at 110 C. for 3 hours. Then a slurry of the product in 1000 mL ethanol was sonicated using a direct immersion titanium tip (60 kHz, 100 W cm.sup.2) at room temperature. The solid PdO/BaSO.sub.4 product was filtered, thoroughly washed with ethanol, dried at room temperature overnight, and dried in a vacuum oven at room temperature for one hour.

(48) FIG. 4 shows E vs. exposure time to 100% H.sub.2 sensing gas for disclosed embodiments including platinated BaSO.sub.4, large scale BaSO.sub.4 that was baked before sonication, and large scale BaSO.sub.4 that was sonicated before being baked. It can be seen that again Pt doping the BaSO.sub.4 supported PdO pigment increases the kinetics of the sensing reaction. FIG. 4 also shows at least for the large scale reactions performed, baking before sonication (e.g., 110 C. for 3 hours) increases the kinetics of the reaction as well as increasing the overall color change as compared to sonication before baking. It is believed that the energy given to the reaction during sonication is sufficient enough for dehydration of palladium hydroxide to palladium oxide in a 10 g BaSO.sub.4batch, but for a larger support mass such as the 250 g BaSO.sub.4 batch used in this Example an initial baking is needed for full conversion to palladium oxide.

Example 7

BaSO4/PdO 3 Wt % PdO Chemochromic Pigment Encapsulated in Clear/White Resin for Hydrogen Gas Detection

(49) BaSO.sub.4 supported PdO pigments (BaSO.sub.4/PdO 3 Wt % PdO) were mixed with Dow 734 silicone resins (a gas permeable polymer) to form an encapsulated BaSO.sub.4/PdO 3 Wt % PdO chemochromic pigment for hydrogen gas testing. 0.2 g of the pigment was ground with 0.8 mL octane, then 6.0 g of clear silicone and 0.7 g of white silicone was added and mixed thoroughly. The mixture was then drawn into a tape for use in detecting hydrogen gas. The E vs. exposure time to 100% H.sub.2 sensing gas shown in FIG. 5 demonstrates excellent E vs. time performance for both the clear and clear/white disclosed encapsulated chemochromic pigment samples.

(50) While various disclosed embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. Numerous changes to the subject matter disclosed herein can be made in accordance with this Disclosure without departing from the spirit or scope of this Disclosure. In addition, while a particular feature may have been disclosed with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular application.

(51) Thus, the breadth and scope of the subject matter provided in this Disclosure should not be limited by any of the above explicitly described embodiments. Rather, the scope of this Disclosure should be defined in accordance with the following claims and their equivalents.

(52) The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms a, an, and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. Furthermore, to the extent that the terms including, includes, having, has, with, or variants thereof are used in either the detailed description and/or the claims, such terms are intended to be inclusive in a manner similar to the term comprising.

(53) Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.