PRODUCTION OF HYDROGEN GAS AND CALCIUM CARBONATE FROM FORMALDEHYDE

Abstract

Disclosed is a method of producing hydrogen (H.sub.2) gas and calcium carbonate from formaldehyde. The method includes combining an aqueous base, formaldehyde, and a transition metal complex having a coordination bond between a transition metal and a leaving group to form a homogeneous aqueous solution having a basic pH, wherein the leaving group dissociates from the transition metal complex in response to light and/or the basic pH of the solution, producing hydrogen (H.sub.2) gas and formate or a salt thereof from the formaldehyde present in the homogeneous aqueous solution, and producing calcium carbonate using the formate or salt thereof as a carbon source.

Claims

1. A method of producing hydrogen and calcium carbonate, the method comprising: (a) combining an aqueous base, formaldehyde, and a transition metal complex having a coordination bond between a transition metal and a leaving group to form a homogeneous aqueous solution having a basic pH, wherein the leaving group dissociates from the transition metal complex in response to light and/or the basic pH of the solution; (b) producing hydrogen (H.sub.2) gas and formate or a salt thereof from the formaldehyde present in the homogeneous aqueous solution; and (c) producing CaCO.sub.3 using the formate or salt thereof as a carbon source.

2. The method of claim 1, wherein step (c) comprises: (i) producing calcium formate (Ca(HCOO).sub.2) by reacting the formate or salt thereof with calcium hydroxide (Ca(OH).sub.2); and (ii) producing CaCO.sub.3 and formaldehyde from the Ca(HCOO).sub.2.

3. The method of claim 2, wherein aqueous base is produced in step (c)(i) and recycled and used in steps (a) and (b).

4. The method of claim 2, wherein the formaldehyde from step (c)(ii) is recycled and used in steps (a) and (b).

5. The method of claim 1, wherein steps (a) and/or (b) are each performed at a temperature from greater than 0° C. to less than 50° C.

6. The method of claim 1, wherein a hydroxide ion replaces the leaving group to form a transition metal-hydroxyl coordination bond, and wherein the transition metal complex having the transition metal-hydroxyl coordination bond reacts with the formaldehyde to produce the hydrogen and formate or salt thereof.

7. The method of claim 6, wherein the transition metal complex is an Fe complex, or an Fe(II) complex.

8. The method of claim 6, wherein the transition metal complex is a Ru complex, or a Ru(III) complex.

9. The method of claim 6, wherein the transition metal complex is an Ir complex, or an Ir(III) complex.

10. The method of claim 6, wherein the transition metal complex is a Cu complex, or a Cu(I) complex.

11. The method of claim 6, wherein the transition metal complex is an Ag complex, or an Ag(I) complex.

12. The method of claim 1, wherein the leaving group dissociates from the transition metal complex in response to light/

13. The method of claim 12, wherein the leaving group is a cyano group (CN.sup.−).

14. The method of claim 13, wherein the transition metal complex is ferricyanide (Fe(CN).sub.6).sup.4−) or a salt thereof.

15. The method of claim 1, wherein the leaving group dissociates from the transition metal in response to the basic pH of the solution.

16. The method claim 1, wherein the leaving group is chloride (Cl.sup.−), fluoride (F.sup.−), bromide (Br.sup.−), iodide (I.sup.−), or astatide (At.sup.−).

17. The method of claim 1, wherein the molar ratio of formaldehyde to base is equal to or less than 2:1.

18. The method of claim 1, wherein the homogeneous aqueous solution has a pH from 8 to 14.

19. The method of claim 1, wherein the formaldehyde and the transition metal complex are fully solubilized in the homogeneous aqueous solution.

20. A homogeneous aqueous solution having a basic pH and being capable of producing hydrogen (H.sub.2) gas and calcium carbonate (CaCO.sub.3), the composition comprising an aqueous base, formaldehyde, and a transition metal complex having a coordination bond between a transition metal and a leaving group, wherein the leaving group dissociates from the transition metal complex in response to light and/or the basic pH of the solution.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.

[0033] FIGS. 1A and 1B are schematics of embodiments of reaction systems of the present invention wherein light (A) or a basic pH (B) is used to disassociate the leaving group from the transition metal complex.

[0034] FIG. 2 are graphs of the amount of products formed or consumed over time during irradiation.

[0035] FIG. 3 are graphs of the hydrogen production and change of pH of the non-catalyzed reaction and the catalyzed reaction over time.

[0036] FIG. 4 is a graph of the change of hydrogen evolution versus the amount of p-formaldehyde added at a constant amount of NaOH.

[0037] FIG. 5 is a graph of the effect of illumination on hydrogen evolution from ferrocyanide catalysis over time.

[0038] FIG. 6 are graphs of the hydrogen flow in ml/min versus time in minutes at various p-formaldehyde and NaOH concentrations.

[0039] FIG. 7 are graphs of the hydrogen production versus time in minutes at various p-formaldehyde and NaOH concentrations.

[0040] FIG. 8 are graphs of hydrogen production in mL versus time in min of the production of hydrogen using various types of water.

[0041] FIG. 9 are graphs of hydrogen evolution versus time using different light sources.

[0042] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and may herein be described in detail. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION

[0043] The present invention provides for an efficient and scalable process for producing hydrogen gas and calcium carbonate from formaldehyde. The process includes combining an aqueous base, formaldehyde, and a transition metal complex catalyst having a coordination bond between a transition metal and a leaving group to form a homogeneous aqueous solution. In response to either light or to the basic pH of the solution, the leaving group can dissociate from the transition metal complex and can be replaced with a hydroxide ion to form a transition metal-hydroxyl coordination bond. The resulting transition metal complex can react with formaldehyde to produce hydrogen and formate or a salt thereof. As illustrated in non-limiting embodiments in the examples, this process can have large turn-over numbers, be operated at relatively low temperatures (e.g., greater than 0° C. to 50° C., preferably room temperatures such as 15° C. to 30° C. or more preferably 20° C. to 25° C.) and under a variety of conditions, thereby allowing for the efficient and scalable production of hydrogen gas and formate (and salt forms thereof). The produced formate (or a salt thereof such as sodium formate) can then be used as a carbon source in the production of calcium carbonate and/or additional formaldehyde by reacting the formate with calcium hydroxide (Ca(OH).sub.2 to form calcium formate (Ca(CHOO).sub.2). Calcium formate can then be converted into calcium carbonate and additional formaldehyde, the latter of which can be recycled. In addition to the low temperature processing conditions, the process of the present invention can limit or even avoid the production of by-products such as carbon dioxide (CO.sub.2).

[0044] The below reaction scheme A provides a non-limiting illustration of a process of the present invention:

##STR00003##

where M is a transition metal having a charge a, Z is a ligand bonded to the metal with a charge of b, L is a leaving group with a charge of x, a is a positive integer from 0 to 6, preferably 0 to 3, b is an negative integer from 0 to −5, x is a negative integer from −1 to −2, y is the total charge of the transition metal complex, and n, o, and p are the atomic ratios of Z, L and OH relative to M, where n is 0 to 6, o is 1 to 3, p is 1, and y is 0, −1, −2, −3, −4, −5, or −6. In a preferred embodiment, y is 0.

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

A. Transition Metal Complex Catalyst

[0046] In some instances, a transition metal complex having a coordination bond between the transition metal and a leaving group acts as a catalyst for the production of formate and H.sub.2 from formaldehyde. The transition metal complex can undergo a reversible dissociation reaction of at least one leaving group. Without wishing to be bound by theory, it is believed that the dissociation of at least one leaving group can produce a transient electrophilic species. A non-limiting example of a transition metal complex catalyst undergoing a dissociation reaction is shown in equation (10) below:

[M.sup.a(Z.sub.n).sup.b(L.sub.o).sup.x].sup.y[M.sup.a(Z.sub.n).sup.b].sup.y+(L.sub.o).sup.x  (10)

where M is a transition metal having a charge a, Z is one or more ligands bonded to the metal with a total charge of b, L is one or more leaving group with total charge of x, and a is a positive integer from 0 to 6, preferably 0 to 3, b is an negative integer from 0 to −5, x is a negative integer from −1 to −2, y is the total charge of the transition metal complex, and n and o are the atomic ratio relative to M, where n ranges from 0 to 6 and o ranges from 1 to 3. In some instances y is 0, −1, −2, −3, −4, −5, or −6.

[0047] The transition metal complex can react with nucleophiles in the reaction mixture, for example, hydroxide ion as shown in equation (11) below.

[(M).sup.a(Z.sub.n).sup.b(L.sub.o).sup.x].sup.y+(OH.sup.−).sub.p[(M).sup.a(Z.sub.n).sup.b(OH.sup.−).sub.p].sup.y  (11)

where M is a transition metal having a charge a, Z is one or more ligands bonded to the metal with a total charge of b, L is one or more leaving group with total charge of x, and a is a positive integer from 0 to 6, preferably 0 to 3, b is an negative integer from 0 to −5, x is a negative integer from −1 to −2, y is the total charge of the transition metal complex, and n, o, and p are the atomic ratio relative to M, where n is ranges from 0 to 6, o ranges from 1 to 3, and p ranges from 0 to 1. In some instances y is 0, −1, −2, −3, −4, −5, or −6.

[0048] Without wishing to be bound by theory, it is believed that the [(M).sup.a(Z.sub.n).sup.b(OH.sup.−).sub.p].sup.y species can react with small organic molecules (e.g., formaldehyde in either intact or hydrated form), followed by reductive elimination of hydrogen and consequent formation of the formate anion. Alternatively, the partly deprotonated form of methanediol (CH.sub.2(OH).sub.2), as obtained from the attack of hydroxide ion top-formaldehyde, may also directly coordinate to the [(M).sup.a(Z.sub.n).sup.b(OH.sup.−).sub.p].sup.y intermediate to form the same species.

[0049] In some instances, the transition metal in the transition metal complex catalyst can be, for example, iron (Fe), ruthenium (Ru), iridium (Ir), or silver (Ag). Preferably, the transition metal is Fe(II), Ru(III), Ir(III), Cu(I), or Ag(I). In some instances, the leaving group (L) can be from two general categories: (1) leaving groups that dissociate from the transition metal complex in response to light and (2), leaving groups that dissociate from the transition metal complex in response to the basic pH of the solution. The former category of leaving groups can include, for example, CN.sup.−. The latter category can include, for example, halides, including fluoride (F.sup.−), chloride (Cl.sup.−), bromide (Br.sup.−), iodide (I.sup.−), or astatide (At.sup.−). Ligand Z can be the same or different than leaving group L. In some embodiments, Z can be an inorganic ligand, an organic ligand or both. Non-limiting examples of organic groups include aromatic groups, a cyano group, a substituted cyano group, an acetate group, a thiocyanate group, an aminidate group, a nitrate group, or combinations thereof. Non-limiting examples of inorganic groups include a halide, phosphate, or both. In some complexes Z is not necessary (e.g., when M has a charge of +1).

[0050] In some instances, the transition metal complex contains iron and has a cyano (CN.sup.−) leaving group. The iron containing catalyst can be a saturated 18-electron complex with Fe(II) in an octahedral, strong ligand-field. The iron containing catalyst can undergo a reversible dissociation reaction of at least one leaving group upon irradiation with visible light. Without wishing to be bound by theory it is believed that the dissociation of at least one leaving group can produce a transient penta-coordinated 16-electron species isolobal with an organic carbocation. Such an electrophilic species can react with nucleophiles. A non-limiting example of such an iron(II) complex is ferrocyanide ([Fe(CN).sub.6].sup.4−). In this instance leaving group CN and ligand Z are the same group. Ferrocyanide is available from many commercial manufacturers, for example, Sigma Aldrich® (USA), as sodium ferrocyanide decahydrate ([(CN).sub.6Fe]Na.sub.4(H.sub.2O).sub.10). A non-limiting example of an iron containing catalyst, ferrocyanide, undergoing a reversible dissociation reaction is shown in equation (12) below.

[Fe(CN).sub.6].sup.4−[Fe(CN).sub.5].sup.3−+CN.sup.−  (12)

The iron containing catalyst can react with nucleophiles in the reaction mixture, for example, hydroxide ion as shown in equation (13) below.

[Fe(CN).sub.5].sup.3−+OH.sup.−[Fe(CN).sub.5(OH)].sup.4−  (13)

[0051] Without wishing to be bound by theory, it is believed that the [Fe(CN).sub.5(OH)].sup.4− species is responsible for the reaction with small organic molecules (e.g., formaldehyde in either intact or hydrated form), followed by reductive elimination of hydrogen and consequent formation of the formate anion as shown in the reaction pathway (B) below. Alternatively, the partly deprotonated form of methanediol (CH.sub.2(OH).sub.2), as obtained from the attack of hydroxide ion to p-formaldehyde, may also directly coordinate to the 16-electron [Fe(CN).sub.5].sup.3− intermediate to form the same species as shown in reaction pathway (B) below, where Z is CN, a is +2, n is 5, and b is −5.

##STR00004##

[0052] A non-limiting example of a transition metal complex undergoing a reversible dissociation reaction under basic pH is shown in reaction pathway (C) below. In a preferred embodiment, Z and L are halides.

##STR00005##

where M is a transition metal having a charge a, Z is a ligand bonded to the metal with a charge of b, L is a leaving group with a charge of x, and a is a positive integer from 0 to 6, preferably 0 to 3, b is an negative integer from 0 to −5, x is a negative integer from −1 to −2, y is the total charge of the transition metal complex, and n, o, and p are the atomic ratio relative to M, where n is 0 to 6, o is 1 to 3, p is 0 to 1, and y is 0, −1, −2, −3, −4, −5, or −6.

B. Reactants and Medium for Production of Hydrogen and Formate

[0053] 1. Reactants

[0054] The reactants in the step of producing formate and H.sub.2 can include formaldehyde, paraformaldehyde, or other organic molecules that release formaldehyde in aqueous solution. Formaldehyde can be formaldehyde, aqueous formaldehyde solutions (for example, 37% in water), para-formaldehyde, or combinations thereof. para-Formaldehyde is the polymerization of formaldehyde with a typical degree of polymerization of 1 to up to 100 units. Aqueous formaldehyde (methanediol) and para-formaldehyde are available from many commercial manufacturers, for example, Sigma Aldrich® (USA). In addition, reactants can include small organic molecules with a terminal aldehyde (RHCO), where R is H or an alkyl group having 1 to 3 carbons. The basic reagent can include a metal hydroxide (MOH or M(OH).sub.2), where M is a alkali or alkaline earth metal. Non-limiting examples of alkali or alkaline earth metals include lithium, sodium, potassium, magnesium, calcium, and barium. In a preferred embodiment, the base is sodium hydroxide (NaOH). The molar ratio of small organic molecule (e.g., formaldehyde) to base is equal to or less than 2:1, 1.9:1, 1.8:1, 1.7:1, 1.6:1, 1.5:1, 1.2:1, 1.1:1, 1:1, 0.5:1 or any range there between.

[0055] 2. Medium

[0056] The production of hydrogen and formate from formaldehyde can be performed in any type of medium that can solubilize the catalyst and reagents. In a preferred embodiment, the medium is water. Non-limiting examples of water include de-ionized water, salt water, river water, canal water, city canal water or the like.

C. Generation of Hydrogen and Formate

[0057] As illustrated in the Examples section, hydrogen and formate can be produced by irradiating, with light, an aqueous composition having a basic pH, formaldehyde, and a transition metal complex catalyst. In preferred instances, the catalyst and the formaldehyde are partially or fully solubilized within the aqueous composition. FIG. 1A is a schematic of an embodiment of a reaction system 100 for producing hydrogen and formate from formaldehyde. System 100 is particularly suited to methods that use a transition metal complex catalyst having a leaving group that dissociates from the transition metal complex in response to light. System 100 includes unit 102, light source 104, and aqueous mixture 106. Unit 102 can be transparent, translucent, or even opaque such as those that can magnify light (e.g., opaque container having a pinhole(s) or those that include a light source within the container). The aqueous homogeneous mixture 106 includes the aqueous formaldehyde (methanediol), a transition metal complex catalyst, and a base described throughout the specification. Light source 104 can be natural sunlight or an artificial light source such as light from a xenon lamp, a fluorescent light, a light emitting diode (LED), an incandescent light, an ultraviolet (UV) light, or any combination thereof. In certain instances, a combination of natural and artificial light can be used. The transition metal complex catalyst can be used to catalyze the production of formate and hydrogen from the formaldehyde as shown in reaction pathways (A) and (B) above. When the aqueous mixture 106 is exposed the light source 104, H.sub.2 (gas) and formate are produced. Notably, formate and hydrogen are produced only when the solution containing the catalyst is exposed to light. No formate or hydrogen are produced when aqueous formaldehyde and sodium hydroxide solution alone are exposed to light. Thus, it should be understood that you can either illuminate and then add the catalyst or add the catalyst and then illuminate the solution.

[0058] System 100 can also be used in embodiment when the leaving group dissociates in response to the basic pH of the solution (for example, as shown in pathway (C) above). System 100 is particularly suited to methods that use a transition metal complex catalyst having a leaving group that dissociates from the transition metal complex in response to pH. In such a system, system 100 light source 104 is not necessary. Said another way system 100 includes unit 102 and aqueous mixture 106 as shown in FIG. 1B.

[0059] When equimolar solutions of p-formaldehyde and sodium hydroxide are combined, a slow Cannizzaro's disproportionation to MeOH and (HCOO)Na can occur as shown in equation (14) below. The addition of a catalytic amount of the transition metal catalyst containing does not appear to inhibit this disproportionation.

##STR00006##

[0060] The production of formate (e.g., sodium formate) can be as illustrated in the reaction pathways (A), (B), and (C) above and equation (15) below.

CH.sub.2O(l)+NaOH(aq).fwdarw.H.sub.2(g)+HCOONa(aq)ΔGf.sup.9=−91 kJ/mol  (15)

[0061] Without wishing to be bound by the theory, the production of hydrogen is in the homogeneous phase of the aqueous mixture. The spent transition metal complex (e.g., (M).sup.a(Z.sub.n).sup.b) can be precipitate or be precipitated from the solution by addition of acid to increase the pH of the solution. The resulting precipitate can be removed, or substantially removed, through known solid/liquid filtration methods (e.g., centrifugation, filtration, gravity settling, etc.). In some embodiments, the transition metal complex is not removed or is partially removed from the solution. The formate (or formic acid), which is also dissolved in the solution, can then be used as a carbon source for production of calcium carbonate.

[0062] Notably, no carbon dioxide is formed during the production of formate and hydrogen. Thus, the process can be considered a “green” process. Furthermore, system 100 does not require the use of an external bias or voltage source, although one can be used if so desired. Further, the efficiency of system 100 allows for one to use formaldehyde as a hydrogen storage agent and formate as a carbon source.

D. Generation of Calcium Formate

[0063] In some embodiments, a step in the production of calcium carbonate from formaldehyde includes production of calcium formate from formate or a salt thereof by reacting the formate or salt thereof with calcium hydroxide (Ca(OH).sub.2) as shown in equation (16), using sodium formate as an example of a salt of formate.

2Na(HCOO)+Ca(OH).sub.2.fwdarw.Ca(HCOO).sub.2+2NaOH  (16)

This process can be performed by any appropriate method known to those of ordinary skill in the art. In a non-limiting example, a basic aqueous sodium formate solution (e.g., pH of 12 to 13) can be at room temperature (e.g., 15° C. and 30° C., preferably 20° C. to 25° C.). Calcium hydroxide can be added to the solution to convert sodium formate to calcium formate and NaOH. The NaOH can then be recycled and used in the overall reaction (See, e.g., reaction scheme A).

[0064] In some embodiments, calcium formate can also be produced from formate or a salt thereof by an ion exchange process, such as that described in U.S. Pat. No. 6,492,551. In this process, formate ions from any source, including sodium formate, are bound to an anion exchange material. Calcium formate can be eluted from the material by feeding a calcium salt of an anion that replaces the formate anion bound to the anion exchange material. The anion that replaces the formate can be, for example, chloride (Cl.sup.−), and the calcium salt can be calcium chloride (CaCl.sub.2).

E. Generation of Calcium Carbonate and Formaldehyde

[0065] Calcium carbonate and formaldehyde can be produced from calcium formate by any appropriate method known to those of ordinary skill in the art. In a non-limiting example, this can be achieved by heating calcium formate to a temperature of approximately 250° C. to 350° C., preferably around 300° C. to produce calcium carbonate and formaldehyde as shown in equation (17).

Ca(HCOO).sub.2(solid).fwdarw.CaCO.sub.3(solid)+H.sub.2CO.sub.(gas)  (17)

The formaldehyde gas can be captured and dissolved in water to be used in further production of hydrogen and calcium carbonate.

F. Methanol Feedstock

[0066] In some instances, methanol can be used as a feedstock for the production of hydrogen and calcium carbonate. Methanol can be oxidized to form formaldehyde by, for example, the Formox® (Formox AB, Sweden) process. In this process, methanol and oxygen react in the presence of a catalyst such as silver metal or a mixture of an iron oxide with molybdenum and/or vanadium to form formaldehyde. When the catalyst is a mixture of iron oxide with molybdenum and/or vanadium, methanol and oxygen react at about 300 to 400° C. to produce formaldehyde according to equation (18) below:

CH.sub.3OH+½O.sub.2.fwdarw.CH.sub.2O+H.sub.2O  (18)

The formaldehyde can then be used as described above in the production of hydrogen and calcium carbonate.

EXAMPLES

[0067] 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

Materials and Testing Procedures for Production of Hydrogen from Formaldehyde

[0068] Materials.

[0069] Paraformaldehyde, 37% formaldehyde solution, and sodium ferrocyanide decahydrate, acetamide were purchased from Sigma-Aldrich® (USA). Formic acid was purchased from Acros Organics (BELGIUM). Sodium thiosulfate was purchased from Oakwood Chemicals (USA). Iodine was purchased from Strem Chemicals, Inc. (USA). Citric acid was purchased from Fisher Scientific (USA). Acetic anhydride was purchased from VWR International (USA). Chemicals were used without further purification. If not specifically mentioned, all reactions were carried out in distilled water without degassing or other modifications.

[0070] Analytical Equipment.

[0071] pH measurements were taken with a Hanna HI 2210 benchtop pH meter with a general purpose combination pH electrode, both purchased from Sigma-Aldrich®. Powder XRD diffractograms were obtained on a Rigaku Ultima IV diffractometer set to 2 2θo/min from 10-70 2θo. UV-Vis spectra were obtained on a Specmate UV-1100 spectrometer. Infrared spectra were obtained on a Nicolet 6700 FTIR with diamond ATR between 650-4000 cm.sup.−1, at 128 scans with a resolution of 4 cm.sup.−1.

[0072] Product Analysis.

[0073] H.sub.2, CO.sub.2, CO and O.sub.2 gas identification and detection was carried out with an Agilent 7820A GC equipped with a thermal conductivity detector (TCD), using an Agilent GS-CarbonPlot column (for CO.sub.2) or Agilent HP-Molesieve column (for all other gasses).

[0074] Determination of Reaction Kinetics.

[0075] The gaseous outflow of the reaction mixture was hooked up to a Restek ProFLOW 6000 Electronic Flow-meter connected to a computer.

[0076] Determination of pH.

[0077] Two identical solutions of 66.6 mmol of p-formaldehyde and 375 mmol of NaOH were prepared simultaneously and were measured to have identical pH values. Both solutions were then illuminated and to one solution, 2 mmol of sodium ferrocyanide was added, and the pH values were measured at regular intervals for 300 minutes.

[0078] Determination of Formate Concentration.

[0079] Concentration of dissolved formate was determined according to a modified colorimetric procedure by Sleat et al. (Appl. Environ. Microbiol. 1984, 47, 884). An aliquot of the reaction mixture (0.5 mL) was added to acetamide (10%, 2 mL) and citric acid (0.05%) dissolved in a 1:1 mixture of isopropanol and water. To the test mixture, sodium acetate (0.1 mL of 30%) and of acetic anhydride (7 mL) were added. The test mixture was shaken and incubated at room temperature for 60 minutes and measured spectrophotometrically at 510 nm. The concentration was determined against a standard curve.

[0080] Determination of Formaldehyde Concentration.

[0081] Formaldehyde concentrations were determined through iodine/sodium thiosulfate titrations. To an aliquot of the reaction mixture (10 mL), de-ionized water (20 mL), iodine (25 mL, 0.05M/L in methanol) and sodium hydroxide (10 mL, 1.0M) were added and stirred for 10 minutes followed by the addition of sulfuric acid (15 mL, 1.0M). The sample solution was then titrated with sodium thiosulphate, with addition of a 1% starch solution as an indicator once the solution turned light yellow. The concentration of formaldehyde was then calculated by a standard curve.

[0082] Isolation of Iron Oxide.

[0083] Iron oxide was collected after allowing a standard reaction to continue for 5 days with a continuous addition of para-formaldehyde and sodium hydroxide. A brown-red precipitate slowly formed which was centrifuged, washed and dried.

Example 2

Generation of Hydrogen and Formate from Para-Formaldehyde

[0084] Formaldehyde (50 mmol of p-formaldehyde or 37% formaldehyde solutions) was added to NaOH (250 mmol) in H.sub.2O. The photocatalyst, sodium ferrocyanide ([(CN).sub.6Fe]Na.sub.4(H.sub.2O).sub.10), (500 μmol (1 mol %)) was added to the solution. The reaction mixture was illuminated with a 300 W Xe arc-lamp and the evolution of hydrogen was monitored. In this experiment 825 mL of hydrogen was generated over a 300 minute time period. The disappearance of formaldehyde was monitored by the titration method described above, while the formation of sodium formate was monitored by the colorimetric method described above. FIG. 2 are graphs of formation of products versus reagent consumption during irradiation. Data 202 is the amount of formaldehyde over time. Data 204 is the amount formate formed over time, and data 206 is the amount of hydrogen produced over time. As shown in FIG. 2, hydrogen and formate were both produced, which indicated that formaldehyde and hydroxide ion were both consumed in the reaction process.

Example 3

Catalytic Versus Non-Catalytic Generation of Hydrogen from Formaldehyde

[0085] Non-Catalyzed Procedure.

[0086] Formaldehyde (66.6 mmol of p-formaldehyde) was added to NaOH (375 mmol) in H.sub.2O. The reaction mixture was illuminated with a 300 W Xe arc-lamp. The change in pH was measured. No hydrogen evolution was detected. No catalyst was added to this solution.

[0087] Catalyzed Procedure.

[0088] Formaldehyde (66.6 mmol of p-formaldehyde) was added to NaOH (375 mmol) in H.sub.2O. The photocatalyst, sodium ferrocyanide ([(CN).sub.6Fe]Na.sub.4(H.sub.2O).sub.10), (2 mmol) was added to the solution (total volume 300 mL). The reaction mixture was illuminated with a 300 W Xe arc-lamp, the evolution of hydrogen was monitored, and the change in pH was measured.

[0089] FIG. 3 are graphs of the change of pH of the non-catalyzed reaction and the catalyzed reaction over time. Data 302 is the non-catalyzed reaction (“blank”). Data 304 is the catalyzed reaction. Data 306 is the hydrogen production from the catalyzed reaction. As shown in FIG. 3, the pH in both a catalyzed standard H.sub.2 evolving reaction and a non-catalyzed reaction decrease over time. The pH of the catalyzed reaction had a faster rate with respect to H.sub.2 production versus the non-catalyzed reaction (time 0 until no more hydrogen evolution was detected, about 30 min, See, FIG. 3), but over time the rate of pH change of the catalyzed reaction became similar to the rate of pH change of the non-catalyzed reaction. Without wishing to be bound by theory it is believed that decrease in the pH after no more hydrogen evolution was detected (about 30 min.) is due to the Cannizzaro reaction (See, equation 11). In addition, without wishing to be bound by theory, it is believed that the initial rate of pH change at the beginning of the catalyzed reaction indicated that hydroxide ion is also required to activate the catalyst.

Example 4

Variation of Formaldehyde Concentration

[0090] p-Formaldehyde in the amounts listed in Table 1 were added to NaOH (375 mmol) in H.sub.2O. The photocatalyst, sodium ferrocyanide ([(CN).sub.6Fe]Na.sub.4(H.sub.2O).sub.10), (0.5 mmol) was added to the solution (total volume 250 mL). The amount of hydrogen evolution was measured. The reaction mixture was illuminated with a 300 W Xe arc-lamp and the evolution of hydrogen was monitored. FIG. 4 is a graph of the change of hydrogen evolution versus the amount ofp-formaldehyde added at a constant amount of NaOH. From the data in FIG. 4, at low initial concentrations of p-formaldehyde, the conversion to hydrogen was deemed to be as high as 100%, but decreased when the concentration levels of the p-formaldehyde increased. The maximum total productivity was reached when the amount of p-formaldehyde was approximately equimolar with NaOH (p-formaldehyde/NaOH=1.2). At higher ratios hydrogen production was not as pronounced.

[0091] p-Formaldehyde in concentrations listed in Table 1 was added to 300 mL of 1.125 M NaOH (about 0.34 mmol) in H.sub.2O. The photocatalyst, sodium ferrocyanide ([(CN).sub.6Fe]Na.sub.4(H.sub.2O).sub.10), (0.6 mmol) was added to the solution and the evolution of hydrogen was monitored. The reaction mixture was illuminated with a 300 W Xe arc-lamp. The amount of hydrogen evolution was measured. Table 1 is a listing of the amount of hydrogen evolved and the catalyst turnover.

TABLE-US-00001 TABLE 1 Formaldehyde Hydrogen (mmoles) evolved (mmoles) Yield (%) Turnovers 0.33* 0.33 100% 0.56 3.33* 3.15 94% 5.25 6.67* 5.23 78% 8.72 33.33* 19.62 59% 32.70 66.67* 34.13 51% 56.88 333.33* 69.90 21% 116.49 375.00** 59.35 16% 98.92 *Commercial para-formaldehyde. **Commercial Formalin solution.

Example 5

[0092] (Effect of Radiation)

[0093] Formaldehyde (66.6 mmol, p-formaldehyde) was added to NaOH (325 mmol) in H.sub.2O. The photocatalyst, sodium ferrocyanide ([(CN).sub.6Fe]Na.sub.4(H.sub.2O).sub.10), (2 mmol) was added to the solution (total volume 300 mL). The reaction mixture was illuminated with a 300 W Xe arc-lamp and the evolution of hydrogen was monitored. FIG. 5 is a graph of the effect of illumination on hydrogen evolution from ferrocyanide catalysis over time. The portion of the lines that have a slope (data 502, Δ) represents periods when catalyst is illuminated and the substantially flat portions of the line (data 504,) represents periods when catalyst is in the dark. From the data in FIG. 5, it was determined that when irradiation with visible light was interrupted, the hydrogen evolution stopped and it was either restarted or arrested by intermittently turning the light on and off. In other words, in some instances, the catalytic system of the present invention is light-switchable.

Example 6

Hydrogen Rate of Formation and Production

[0094] Formaldehyde (50 mmol of p-formaldehyde) was added to NaOH (250 mmol) in H.sub.2O. The photocatalyst, sodium ferrocyanide ([(CN).sub.6Fe]Na.sub.4(H.sub.2O).sub.10), (0.5 mmol) was added to the solution (total volume 300 mL). The reaction mixture was illuminated with a 300 W Xe arc-lamp and the evolution of hydrogen was monitored. An initial 0.25 moles of NaOH was added to both solutions to ensure that the pH was suitable for deprotonation of methanediol. Every 30 minutes, 50 mmol p-formaldehyde and either 50 mmol or 200 mmol NaOH were added. The hydrogen rate of formation (FIG. 6) and productivity (FIG. 7) were monitored by regularly adding p-formaldehyde and NaOH in both a 1:5 and 1:1 molar ratio. FIG. 6 are graphs of the hydrogen flow in ml/min versus time in minutes at various p-formaldehyde and NaOH concentrations. Data 602 is at 50 mmol of NaOH and data 604 is at 200 mmol of NaOH. FIG. 7 are graphs of the hydrogen production versus time in minutes at various p-formaldehyde and NaOH concentrations. Data 702 is at 50 mmol of NaOH and data 704 is at 200 mmol of NaOH. Elevated hydrogen evolution rates were observed when the ratio of p-formaldehyde to NaOH was 1:5, which slowed before the next sample was added. However, with each addition of p-formaldehyde and NaOH, the maximum rate decreased rapidly and after the 10.sup.th addition of regents, the rate was zero. This drop was attributed to decomposition of the catalyst to Fe.sub.2O.sub.3 in highly basic conditions. As shown in FIG. 7, addition of 1:1 p-formaldehyde to NaOH portions (data 602) resulted in a steady productivity being reached, with no decline of catalytic activity for 350 minutes. Within each addition, a reduction in the initial spike of hydrogen production is observed, which stabilizes into a nearly continuous release of 10 mL of hydrogen per minute.

Example 7

Effect of Water Purity on Catalytic Activity

[0095] Formaldehyde (66.6 mmol of p-formaldehyde) was added to NaOH (375 mmol) in H.sub.2O. The photocatalyst, sodium ferrocyanide ([(CN).sub.6Fe]Na.sub.4(H.sub.2O).sub.10), (3 mmol) was added to the solution (total volume 300 mL). Three types of water de-ionized water, river water and salt water were evaluated. FIG. 8 are graphs of hydrogen production in mL versus time in min of the production of hydrogen using various types of water. Data 802 is hydrogen production using de-ionized water, data 804 is hydrogen production using city canal water, and data 806 is hydrogen production using salt water. As determined from the data in FIG. 8, the reaction rates and final production from the three sources were nearly identical. Thus, the choice of water source (i.e., distilled water, 3.5% NaCl solutions (to match the average salinity of the ocean), or water taken directly from city canal water), had no significant effect on the activity of the catalyst.

Example 8

Long Range Catalytic Runs

[0096] Formaldehyde (0.5 mol of p-formaldehyde) was added to NaOH (0.25 mol) in H.sub.2O. The sodium ferrocyanide photocatalyst ([(CN).sub.6Fe]Na.sub.4(H.sub.2O).sub.10, 120 mg) was added to the solution (total volume 300 mL). The reaction mixture was run twice with two different light sources, a 300 W Xe arc-lamp and a Hg lamp. The evolution of hydrogen was monitored. FIG. 9 are graphs of hydrogen evolution versus time using different light sources. Data 902 is the generation of hydrogen using an embodiment of the present invention using a Xenon arc-lamp as a light source. Data 904 is the generation of hydrogen using an embodiment of the present invention using the Hg lamp as a light source. From the data in FIG. 9, it was determined that the reactions were uninterruptedly carried out for 16 h with periodical additions of NaOH/p-formaldehyde every 30 min. Over time the catalytic system slowly decayed after having produced about 4.8 L of pure hydrogen (14.5% based on p-formaldehyde). At this stage a significant amount of Fe.sub.2O.sub.3 become visible, which was isolated and characterized as described in Example 1.