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US4298439A Expired / Lapsed US ⏱️ 0.0 years remaining

Producing long life disproportionation products from a photo redox agent useful as a reducing medium for water, and the like

Assignee: Research Foundation of City University of New York
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Filing: 1980-08-11
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Granted: 1981-11-03
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Expires: 2000-08-11
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Abstract

Abstract The lifetime of the photo redox induced disproportionation products of ruthenium polypiridine complexes is significantly increased from about two milliseconds in a liquid phase to greater than thirty-six hours by depositing the complexes in the pores of thirsty glass, thus making possible their use in chemical reactions such as the reduction of water to produce hydrogen at room temperatures. A photochemical reaction system is thereby formed within the situs of the porous glass which adsorbs the photo redox agent and permits diffusion of hydrogen out as an end product while retaining its transparency and characteristics for long periods of use. The porous glass medium withstands high temperatures and processes of organizing the reaction system by depositing as complementary layers various agents and catalysts necessary in a chemical reaction system from solutions and at temperatures otherwise incompatible with liquid redox agents or other site materials.

Inventors

  • 👤 Harry D. Gafney

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-08 15:03
CPC Classifications
C; C01; C01B; C01B3/00; C01B3/02; C01B3/04; C01B3/042; B; B01; B01J; B01J19/00; B01J19/08; B01J19/12; B01J19/122; Y; Y02; Y02E; Y02E60/00; Y02E60/30; Y02E60/36

Claims Analysis

Total Claims: 27
Claim 1
Independent Claim 68 words
The method of disproportionately increasing the lifetime of photoinduced disproportionation products of a photo redox agent comprising the steps of, introducing the photo redox agent into the pores of a transparent porous sorbent medium presenting an array of internal cavities, and producing long life disporportionation products by transmission of photo energy into said medium to react with the photo redox agent situate in the pores of said medium.
Claim 2
Independent Claim 68 words
The method of disproportionately increasing the lifetime of photoinduced disproportionation products of a photo redox agent comprising the steps of, introducing the photo redox agent into the pores of a transparent porous sorbent medium presenting an array of internal cavities, and producing long life disporportionation products by transmission of photo energy into said medium to react with the photo redox agent situate in the pores of said medium.
Claim 3
Dependent Claim 32 words
The method defined in claim 1 wherein the agent introduced into the medium is a polypyridene complex fluid solution adsorbed into the medium and vacuum dried to remove substantially all the solvent.
Claim 4
Dependent Claim 26 words
The method defined in claim 1 wherein the medium into which the agent is introduced is porous glass containing a random three dimensional array of cavities.
Claim 5
Dependent Claim 17 words
The method of claim 3 wherein the glass has cavity sizes of the order of 70 A°.
Claim 6
Dependent Claim 27 words
The method defined in claim 1 including the further step of introducing a compound into the porous medium with said agent which reacts with the disproportionation products.
Claim 7
Dependent Claim 22 words
The method defined in claim 5 wherein the compound is water which reacts to effect dissociation of hydrogen from the water molecule.
Claim 8
Dependent Claim 31 words
The method defined in claim 6 including the step of introducing the catalyst PtO 2 as a surface deposit in the cavities of said medium to increase the yield of hydrogen.
Claim 9
Dependent Claim 57 words
The method defined in claim 7 wherein the medium is porous glass including the introduction of the catalyst into the medium by the steps of, adsorbing into the glass an aqueous solution of platinic acid and NaOOCH at 0° C., and heating the glass to the order of 200° C. to reduce the solution to platinum black.
Claim 10
Dependent Claim 37 words
The method defined in claim 6 including the step of introducing the catalyst ruthenium oxide into the medium as a surface deposit in the cavities to increase the oxidation yield of the oxygen molecule from the water.
Claim 11
Dependent Claim 47 words
The method defined in claim 9 wherein the medium is porous glass including the introduction of the catalyst into the medium by the steps of, adsorbing an aqueous solution of RuCl 3 into the glass and heating the glass in air at 120° C. for one week.
Claim 12
Dependent Claim 72 words
The method defined in claim 5 including the introduction of the compound into the medium by the steps of, saturating the pores of a glass medium having 10 -6 moles of Ru(bpy) 3 Cl 2 per gram of glass with distilled water after coating the cavity surfaces within the glass with a catalyst from the group Pt, PtO and PtO 2 in a quantity not seriously affecting the transparency of the glass.
Claim 13
Dependent Claim 24 words
The method defined in claim 11 including the recovery of hydrogen by the steps of, diffusing the hydrogen from the pores of the glass.
Claim 14
Dependent Claim 20 words
The method of claim 5 wherein the medium reacting with the disporportionation products of the redox agent is methyl viologen.
Claim 15
Dependent Claim 48 words
The method defined in claim 1 including the introduction of water into the medium in the presence of the redox agent by the steps of, depositing the redox agent and a catalyst in the cavities of the medium, and thereafter adsorbing water into the pores of the glass.
Claim 16
Dependent Claim 38 words
The method defined in claim 1 wherein the step introducing the photo redox agent comprises the sub steps of adsorbing a liquid solution of Ru(bpy) 3 Cl 2 into the glass and vacuum drying to remove the liquid.
Claim 17
Dependent Claim 71 words
A photochemical reaction system comprising in combination, a transparent porous sorbent medium having an array of internal cavities, and a solution introduced within the cavities of the medium including a photo redox agent and a chemical reacting with photoinduced disproportionation products of the photo redox agent, all retained within said medium without significant loss of transparency thereby to permit transmission of photo energy into the site of the photo redox agent.
Claim 18
Dependent Claim 71 words
A photochemical reaction system comprising in combination, a transparent porous sorbent medium having an array of internal cavities, and a solution introduced within the cavities of the medium including a photo redox agent and a chemical reacting with photoinduced disproportionation products of the photo redox agent, all retained within said medium without significant loss of transparency thereby to permit transmission of photo energy into the site of the photo redox agent.
Claim 19
Dependent Claim 12 words
The reaction system of claim 16 wherein the medium is thirsty glass.
Claim 20
Dependent Claim 15 words
The reaction system of claim 16 wherein the redox agent is a ruthenium bipyridene complex.
Claim 21
Dependent Claim 11 words
The reaction system of claim 18 wherein the chemical is water.
Claim 22
Dependent Claim 11 words
The reaction system of claim 16 wherein the chemical is water.
Claim 23
Dependent Claim 20 words
The reaction system of claim 20 including a platinum catalyst deposited on the surface area of the sorbent medium cavities.
Claim 24
Dependent Claim 21 words
The reaction system of claim 20 including the catalyst ruthenium oxide deposited on the surface area of the sorbent medium cavities.
Claim 25
Independent Claim 76 words
The method of employing thirsty glass as a chemical reaction situs comprising the steps of, depositing on the walls of the cavities within said glass from a solution passed into the pores of the glass a first chemical and withdrawing the solution, thereafter depositing by a like procedure on the walls of the cavities to supplement the deposits of first chemical a second chemical, and introducing an agent into the cavities to react with said chemicals.
Claim 26
Independent Claim 76 words
The method of employing thirsty glass as a chemical reaction situs comprising the steps of, depositing on the walls of the cavities within said glass from a solution passed into the pores of the glass a first chemical and withdrawing the solution, thereafter depositing by a like procedure on the walls of the cavities to supplement the deposits of first chemical a second chemical, and introducing an agent into the cavities to react with said chemicals.
Claim 27
Dependent Claim 53 words
The method as defined in claim 23 wherein the reaction is a photochemical reaction and one of the chemicals deposited is responsive to photo energy to change its state, including the step of passing photo energy through the glass to reach the chemicals deposited in the cavities thereby to induce the photochemical reaction.

References Cited (Backward Citations)

US4173521A Cited
US4045315A Cited
US4060468A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1984-11-02 1985-05-04 1985-11-03 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1988-11-02 1989-05-04 1989-11-03 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1992-11-02 1993-05-04 1993-11-03 $7700.00 Window Closed / Lapsed

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