Methods of enhanced hydrogen generation from iron-bearing rocks

Abstract

Disclosed herein are methods of enhanced hydrogen generation from iron-bearing rocks. For example, disclosed herein are methods of enhanced hydrogen generation from iron-bearing rocks, the methods comprising: contacting an iron-bearing rock with an iron solubilizer, a catalyst solubilizer, an intermediary catalyst-iron-compound, and / or a catalyst (e.g., in an aqueous solution), thereby increasing the rate of hydrogen production and / or lowering the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said iron solubilizer, catalyst solubilizer, intermediary catalyst-iron-compound, and / or catalyst. Also disclosed herein are methods of use of hydrogen produced by any of the methods disclosed herein.

Description

[0001] METHODS OF ENHANCED HYDROGEN GENERATION FROM IRON-BEARING ROCKS CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 63 / 708,972 filed October 18, 2024, which is hereby incorporated herein by reference in its entirety. STATEMENT OF GOVERNMENT SUPPORT This invention was made with government support under grant number DE-AR0001895 awarded by the U.S. Department of Energy (DOE). The government has certain rights in the application. BACKGROUND H2production currently depends on energy-intensive, high CO2-emission steam reforming methods to meet global demand; less than 0.7% of H2production is sourced from low- CO2-emission sources, and >90% of global H2is sourced from fossil fuels that yield 7.5-12 tons of CO2 per ton H2 produced. New low CO2-emission H2 resources are necessary to meet global H2 demand. The compositions, devices, and methods discussed herein address these and other needs. SUMMARY In accordance with the purposes of the disclosed compositions, methods, and devices as embodied and broadly described herein, the disclosed subject matter relates to methods of enhanced hydrogen generation from iron-bearing rocks. For example, disclosed herein are methods of enhanced hydrogen generation from iron- bearing rocks, the methods comprising: contacting an iron-bearing rock with an aqueous solution comprising an iron solubilizer, a catalyst solubilizer, and / or a catalyst. The iron solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of iron from the iron-bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen. The catalyst solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron-bearing rock, when present, thereby increasing the availability of said mineral-hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The methods thereby increasing the rate of hydrogen production and / or lowering the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said aqueous solution. Also disclosed herein are methods of enhanced hydrogen generation from iron-bearing rocks, the methods comprising: contacting an iron-bearing rock with an iron solubilizer, a catalyst solubilizer, an intermediary catalyst-iron-compound, and / or a catalyst. The iron solubilizer, when present, increases the dissolution rate and solubility of iron from the iron- bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen. The catalyst solubilizer, when present, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron-bearing rock, when present, thereby increasing the availability of said mineral-hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The methods thereby increasing the rate of hydrogen production and / or lowering the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said iron solubilizer, catalyst solubilizer, intermediary catalyst-iron-compound, and / or catalyst. Also disclosed herein are methods of enhanced hydrogen generation from iron-bearing rocks, the methods comprising: contacting an iron-bearing rock with an aqueous solution comprising an iron solubilizer, a catalyst solubilizer, an intermediary catalyst-iron-compound, and / or a catalyst. The iron solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of iron from the iron-bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen. The catalyst solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron-bearing rock, when present, thereby increasing the availability of said mineral-hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The methods thereby increasing the rate of hydrogen production and / or lowering the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said aqueous solution. In some examples, the temperature of reaction is 300°C or less. In some examples, the temperature of reaction is lowered to 125°C or less. In some examples, the temperature of reaction is lowered to 100°C or less. In some examples, the temperature of reaction is 90°C or less. In some examples, the temperature of reaction is 75°C or less. In some examples, the hydrogen production rate is increased to greater than 5 × 104kg / sec. In some examples, said contacting occurs in situ with the iron-bearing rock. In some examples, the iron-bearing rock is part of a subsurface formation and / or geological formation. In some examples, the iron-bearing rock comprises (ultra)mafic rock (e.g., mafic rock and / or ultramafic rock). In some examples, the iron-bearing rock comprises mafic rock. In some examples, the iron-bearing rock comprises (ultra)mafic peridotite, (ultra)mafic pyroxenite, (ultra)mafic hornblendite, (ultra)mafic dunite, or a combination thereof. In some examples, the iron-bearing rock comprises (ultra)mafic peridotite, (ultra)mafic pyroxenite, (ultra)mafic basalt, Archaean banded iron formations, (ultra)mafic dunite, or a combination thereof. In some examples, the iron-bearing rock comprises olivine, pyroxene, amphibole, or a combination thereof. In some examples, the iron-bearing rock comprises olivine, pyroxene, or a combination thereof. In some examples, the iron-bearing rock comprises banded iron formations. In some examples, the iron solubilizer is present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the iron solubilizer. In some examples, the iron solubilizer comprises a halogen containing compound. In some examples, the iron solubilizer comprises an acid. In some examples, the method further comprises injecting CO2to create the iron solubilizer in situ. In some examples, the iron solubilizer comprises an acid and the method further comprises injecting CO2 to create the iron solubilizer in situ. In some examples, the catalyst solubilizer is present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst solubilizer. In some examples, the iron solubilizer and the catalyst solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the iron solubilizer and the catalyst solubilizer. In some examples, the mineral-hosted catalyst comprises a transition metal, such as W, Mo, Nb, Ta, Re, Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof. In some examples, the mineral-hosted catalyst comprises Ni, Co, Mo, V, or a combination thereof. In some examples, the mineral-hosted catalyst comprises a transition metal, such as Ni, Cu, Pt, Pd, or a combination thereof. In some examples, the mineral-hosted catalyst comprises Ni. In some examples, the mineral-hosted catalyst comprises a platinum group element, such as Pt, Pd, or a combination thereof. In some examples, the catalyst is present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst. In some examples, the catalyst and the iron solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst and the iron solubilizer. In some examples, the catalyst and the catalyst solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst and the catalyst solubilizer. In some examples, the catalyst, the iron solubilizer, and the catalyst are present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst, the iron solubilizer, and the catalyst solubilizer. In some examples, the catalyst comprises a transition metal, such as W, Mo, Nb, Ta, Re, Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof. In some examples, the catalyst comprises Ni, Co, Mo, V, or a combination thereof. In some examples, the catalyst comprises a transition metal, such as Ni, Cu, Pt, Pd, or a combination thereof. In some examples, the catalyst comprises Ni. In some examples, the catalyst comprises a platinum group element, such as Pt, Pd, or a combination thereof. In some examples, the catalyst comprises a halogen compound, such as a transition metal-halogen compound or a platinum group element-halogen compound, such as a transition metal chloride or a platinum group element chloride. In some examples, the catalyst comprises a nickel-halogen compound, such as a nickel chloride compound. In some examples, the catalyst comprises NiCl2. In some examples, the intermediary catalyst-iron-compound is present (e.g., in the aqueous solution). In some examples, the intermediary catalyst-iron-compound and the iron solubilizer are present (e.g., in the aqueous solution). In some examples, the intermediary catalyst-iron-compound and the catalyst solubilizer are present (e.g., in the aqueous solution). In some examples, the intermediary catalyst-iron-compound and the catalyst are present (e.g., in the aqueous solution). In some examples, the intermediary catalyst-iron-compound, the iron solubilizer, and the catalyst solubilizer are present (e.g., in the aqueous solution). In some examples, the intermediary catalyst-iron-compound, the iron solubilizer, and the catalyst are present (e.g., in the aqueous solution). In some examples, the intermediary catalyst-iron- compound, the catalyst solubilizer, and the catalyst are present (e.g., in the aqueous solution). In some examples, the iron solubilizer, the catalyst solubilizer, the intermediary catalyst-iron- compound, and the catalyst are present (e.g., in the aqueous solution). In some examples, the aqueous solution has an alkaline pH. In some examples, the method further comprises collecting the produced hydrogen and optionally storing the produced hydrogen. In some examples, the method further comprises collecting the solubilized iron, solubilized mineral-hosted catalyst, the intermediary catalyst-iron-compound, and / or aqueous catalyst, and optionally recycling them to repeat any of the methods disclosed herein. In some examples, the method further comprises collecting the solubilized iron, solubilized mineral-hosted catalyst, and / or aqueous catalyst, and optionally recycling them to repeat any of the methods disclosed herein. In some examples, the method does not produce a significant amount of greenhouse gases, such as CO2, for example wherein the method produces 1 kilogram or less of CO2equivalent (CO2eq) per kilogram of produced H2. In some examples, the method is economical, for example maintaining costs to $1 per kilogram (kg) of produced hydrogen or less. Also disclosed herein are methods of use of hydrogen produced by any of the methods disclosed herein, for example for energy production and / or industrial purposes. In some examples, the method comprises using the produced hydrogen for energy production, energy carrier and fuel, energy storage, and / or industrial purposes, including as industrial feedstock, such as, but not limited to, ammonia, methanol, petroleum refining, metallurgy, electronics, and glass manufacturing. Additional advantages of the disclosed compositions, devices, and methods will be set forth in part in the description which follows, and in part will be obvious from the description. The advantages of the disclosed compositions, devices, and methods will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosed devices and methods, as claimed. The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims. BRIEF DESCRIPTION OF THE FIGURES The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects of the disclosure, and together with the description, serve to explain the principles of the disclosure. Figure 1. (Left panel) Scanning electron microscopy image of partially serpentinized Ni- bearing ultramafic body. (Right panel) Schematic showing diagram of proposed technology scaled to the subsurface. Figure 2. MgO-H2O-SiO2 ternary diagram showing tie-line reactions in ultramafic rocks. Figure 3. Panel A) H2 yield from Fe(OH)2 decomposition with Ni2+at 90°C. Panel B) Black precipitate of iron oxide formation identified with SEM / EDS image. Figure 4. Panel A) Igneous ore deposits associated with the Midcontinental Rift System (MRS), and Panel B) in the Lake Superior and southern Ontario regions. Figure 5. Schematic diagram of serpentinization. Figure 6. Hydration of olivine and oxidation of Fe2+. Figure 7. MgO-H2O-SiO2ternary diagram showing tie-line reactions for the hydration of pyroxenites. Figure 8: Effect of [Fe2+] / [Ni2+] ratio in the solution to H2 yield at 90°C. Square data point represents the H2 yield without the presence of Ni catalyst. Figure 9: Comparison of H2 yield from Fe2+oxidation with and without the presence of VCl3 at 90°C. The pH was measured at room temperature, and the line shows the measured pH curve before and after injecting additional NaOH in the septum-sealed glass bottle. Figure 10: Comparison of H2 yield from Fe2+oxidation in the presence of NiCl2 (aqueous) and NiS (solid) at 90°C. The pH was measured at room temperature, and the line shows the measured pH curve before and after injecting additional NaOH in the septum-sealed glass bottle. Figure 11: H2concentration variation in the headspace of Parr reactor experiments. Black: Uvalde basalt + distilled water + pressurized (150 psi) CO2, Grey: Uvalde basalt + distilled water + pressurized CO2+ NiCl2. Figure 12: Pre-reaction and post-reaction (with CO2-saturated water) minerology changes observed in Uvalde basalt. Figure 13. Measured concentrations of hydrogen produced from experiment for two different grain sizes of San Carlos Olivine showing the effect of NiCl2 catalyst. Figure 14. Measured concentrations of hydrogen produced from five different rock types. Figure 15. Mineralogy and Fe+2content in five of the rocks included in the experimental matrix. DETAILED DESCRIPTION The compositions, methods, and devices described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples included therein. Before the present compositions, methods, and devices are disclosed and described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Also, throughout this specification, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed matter pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon. In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings. Throughout the description and claims of this specification the word “comprise” and other forms of the word, such as “comprising” and “comprises,” means including but not limited to, and is not intended to exclude, for example, other additives, components, integers, or steps. As used in the description and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a composition” includes mixtures of two or more such compositions, reference to “an agent” includes mixtures of two or more such agents, reference to “the component” includes mixtures of two or more such components, and the like. “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not. Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. By “about” is meant within 5% of the value, e.g., within 4, 3, 2, or 1% of the value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. Values can be expressed herein as an “average” value. “Average” generally refers to the statistical mean value. By “substantially” is meant within within 4%, 3%, 2%, or 1%. “Exemplary” means “an example of” and is not intended to convey an indication of a preferred or ideal embodiment. “Such as” is not used in a restrictive sense, but for explanatory purposes. It is understood that throughout this specification the identifiers “first” and “second” are used solely to aid in distinguishing the various components and steps of the disclosed subject matter. The identifiers “first” and “second” are not intended to imply any particular order, amount, preference, or importance to the components or steps modified by these terms. References in the specification and concluding claims to parts by weight of a particular element or component in a composition denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound. A weight percent (wt. %) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included. The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context. Compositions and Methods Disclosed herein are methods of enhanced hydrogen generation from iron-bearing rocks. For example, the methods comprise contacting an iron-bearing rock with an aqueous solution comprising an iron solubilizer, a catalyst solubilizer, and / or a catalyst. The iron solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of iron from the iron-bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen. The catalyst solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron-bearing rock, when present, thereby increasing the availability of said mineral-hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The methods thereby increase the rate of hydrogen production and / or lower the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said aqueous solution. For example, the methods comprise contacting an iron-bearing rock with an iron solubilizer, a catalyst solubilizer, an intermediary catalyst-iron-compound, and / or a catalyst. The iron solubilizer, when present, increases the dissolution rate and solubility of iron from the iron- bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen. The catalyst solubilizer, when present, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron-bearing rock, when present, thereby increasing the availability of said mineral-hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The catalyst, when present, catalyzes the reaction between iron from the iron- bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The methods thereby increase the rate of hydrogen production and / or lower the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said iron solubilizer, catalyst solubilizer, intermediary catalyst-iron-compound, and / or catalyst. For example, the methods comprise contacting an iron-bearing rock with an aqueous solution comprising an iron solubilizer, a catalyst solubilizer, an intermediary catalyst-iron- compound, and / or a catalyst. The iron solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of iron from the iron-bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen. The catalyst solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron- bearing rock, when present, thereby increasing the availability of said mineral-hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen. The methods thereby increase the rate of hydrogen production and / or lower the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said aqueous solution. In some examples, the temperature of reaction is 300°C or less (e.g., 275°C or less, 250°C or less, 225°C or less, 200°C or less, 175°C or less, 150°C or less, 125°C or less, 100°C or less, 95°C or less, 90°C or less, 85°C or less, 80°C or less, 75°C or less, 70°C or less, 65°C or less, 60°C or less, 55°C or less, or 50°C). In some examples, the temperature of reaction is lowered to 125°C or less (e.g., 100°C or less, 95°C or less, 90°C or less, 85°C or less, 80°C or less, 75°C or less, 70°C or less, 65°C or less, 60°C or less, 55°C or less, or 50°C). In some examples, the temperature of reaction is lowered to 100°C or less (e.g., 95°C or less, 90°C or less, 85°C or less, 80°C or less, 75°C or less, 70°C or less, 65°C or less, 60°C or less, 55°C or less, or 50°C). In some examples, the temperature of reaction is 90°C or less (e.g., 85°C or less, 80°C or less, 75°C or less, 70°C or less, 65°C or less, 60°C or less, 55°C or less, or 50°C). In some examples, the temperature of reaction is 75°C or less (e.g., 70°C or less, 65°C or less, 60°C or less, 55°C or less, or 50°C). In some examples, the hydrogen production rate is increased to greater than 5 × 104kg / sec. In some examples, said contacting occurs in situ with the iron-bearing rock. In some examples, the iron-bearing rock is part of a subsurface formation and / or geological formation. In some examples, the iron-bearing rock is part of a subsurface formation and / or geological formation, and said contacting occurs in situ with the iron-bearing rock. In some examples, the iron-bearing rock comprises (ultra)mafic rock. As used herein the term “(ultra)mafic” includes mafic, ultramafic, or combinations thereof. As used herein the term “mafic” includes rocks that contain more than 10% mafic minerals (e.g. minerals containing significant amount of Fe and / or Mg, such as olivine, pyroxene, amphibole, chlorite, epidote, micas, or a combination thereof), whereas ultramafic rocks contain more than 85% mafic minerals. This definition includes altered forms of these rocks, such as metamorphosed variants (e.g., greenschist, amphibole, greenstone) and / or sedimentary and volcaniclastic variants. In some examples, the iron-bearing rock comprises (ultra)mafic peridotite, (ultra)mafic pyroxenite, (ultra)mafic hornblendite, (ultra)mafic dunite, or a combination thereof. In some examples, the iron-bearing rock comprises (ultra)mafic peridotite, (ultra)mafic pyroxenite, (ultra)mafic basalt, Archaean banded iron formations, (ultra)mafic dunite, or a combination thereof. In some examples, the iron-bearing rock comprises mafic rock. In some examples, the iron-bearing rock comprises olivine, pyroxene, amphibole, or a combination thereof. In some examples, the iron-bearing rock comprises olivine, pyroxene, or a combination thereof. In some examples, the iron solubilizer is present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the iron solubilizer. In some examples, the iron solubilizer comprises a halogen containing compound. In some examples, the iron solubilizer comprises an acid. In some examples, the iron-bearing rock comprises banded iron formations. As used herein the term “banded iron formation” includes rocks classified as ironstone. In some examples, the method further comprises injecting CO2 to create the iron solubilizer in situ. In some examples, the iron solubilizer comprises an acid and the method further comprises injecting CO2to create the iron solubilizer in situ. In some examples, the catalyst solubilizer is present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst solubilizer. In some examples, the iron solubilizer and the catalyst solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the iron solubilizer and the catalyst solubilizer. In some examples, the mineral-hosted catalyst comprises a transition metal, such as W, Mo, Nb, Ta, Re, Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof. In some examples, the mineral-hosted catalyst comprises Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof. In some examples, the mineral-hosted catalyst comprises Ni, Co, Mo, V, or a combination thereof. In some examples, the mineral-hosted catalyst comprises Ni, Cu, Pt, Pd, or a combination thereof. In some examples, the mineral-hosted catalyst comprises Ni. In some examples, the mineral-hosted catalyst comprises a platinum group element. Platinum group elements include platinum, palladium, rhodium, ruthenium, iridium, and osmium. In some examples, the mineral-hosted catalyst comprises Pt, Pd, or a combination thereof. In some examples, the catalyst is present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst. In some examples, the catalyst and the iron solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst and the iron solubilizer. In some examples, the catalyst and the catalyst solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst and the catalyst solubilizer. In some examples, the catalyst, the iron solubilizer, and the catalyst solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution includes the catalyst, the iron solubilizer, and the catalyst solubilizer. In some examples, the catalyst comprises a transition metal such as W, Mo, Nb, Ta, Re, Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof. In some examples, the catalyst comprises Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof. In some examples, the catalyst comprises Ni, Co, Mo, V, or a combination thereof. In some examples, the catalyst comprises Ni, Cu, Pt, Pd, or a combination thereof. In some examples, the catalyst comprises Ni. In some examples, the catalyst comprises a platinum group element. In some examples, the catalyst comprises Pt, Pd, or a combination thereof. In some examples, the catalyst comprises a halogen compound. In some examples, the catalyst comprises a transition metal-halogen compound or a platinum group element-halogen compound. In some examples, the catalyst comprises as a transition metal chloride or a platinum group element chloride. Examples of catalysts comprising transitional metal chlorides include, but are not limited to NiCl2, CoCl2, MoCl2, and combinations thereof. In some examples, the catalyst comprises a nickel-halogen compound, such as a nickel chloride compound. In some examples, the catalyst comprises NiCl2. In some examples, the intermediary catalyst-iron-compound is present (e.g., in the aqueous solution). In some examples, the aqueous solution comprises the intermediary catalyst- iron-compound. In some examples, the intermediary catalyst-iron-compound and the iron solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution comprises the intermediary catalyst-iron-compound and the iron solubilizer. In some examples, the intermediary catalyst-iron-compound and the catalyst solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution comprises the intermediary catalyst-iron-compound and the catalyst solubilizer. In some examples, the intermediary catalyst-iron-compound and the catalyst are present (e.g., in the aqueous solution). In some examples, the aqueous solution comprises the intermediary catalyst-iron-compound and the catalyst. In some examples, the intermediary catalyst-iron-compound, the iron solubilizer, and the catalyst solubilizer are present (e.g., in the aqueous solution). In some examples, the aqueous solution comprises the intermediary catalyst-iron-compound, the iron solubilizer, and the catalyst solubilizer. In some examples, the intermediary catalyst-iron-compound, the iron solubilizer, and the catalyst are present (e.g., in the aqueous solution). In some examples, the aqueous solution comprises the intermediary catalyst-iron-compound, the iron solubilizer, and the catalyst. In some examples, the intermediary catalyst-iron-compound, the catalyst solubilizer, and the catalyst are present (e.g., in the aqueous solution). In some examples, the aqueous solution comprises the intermediary catalyst-iron-compound, the catalyst solubilizer, and the catalyst. In some examples, the iron solubilizer, the catalyst solubilizer, the intermediary catalyst- iron-compound, and the catalyst are present (e.g., in the aqueous solution). In some examples, the aqueous solution comprises the iron solubilizer, the catalyst solubilizer, the intermediary catalyst-iron-compound, and the catalyst. In some examples, the method is performed at acidic pH (e.g., pH from 0 to less than 7), neutral pH (e.g., pH 7), or alkaline pH (e.g., pH greater than 7 to 14). In some examples, the aqueous solution has an acidic pH (e.g., pH from 0 to less than 7), a neutral pH (e.g., pH 7), or an alkaline pH (e.g., pH greater than 7 to 14). In some examples, the aqueous solution has an alkaline pH. In some examples, the aqueous solution has a pH of greater than 7 (e.g., 7.5 or more, 8 or more, 8.5 or more, 9 or more, 9.5 or more, 10 or more, 10.5 or more, 11 or more, 11.5 or more, 12 or more, 12.5 or more, 13 or more, or 13.5 or more). In some examples, the aqueous solution has a pH of 14 or less (e.g., 13.5 or less, 13 or less, 12.5 or less, 12 or less, 11.5 or less, 11 or less, 10.5 or less, 10 or less, 9.5 or less, 9 or less, 8.5 or less, 8 or less, or 7.5 or less). The pH of the aqueous solution can range from any of the minimum values described above to any of the maximum values described above. For example, the aqueous solution can have a pH of from greater than 7 to 14 (e.g., an alkaline pH) (e.g., from greater than 7 to 10.5, from 10.5 to 14, from greater than 7 to 9, from 9 to 11, from 11 to 14, from greater than 7 to 12, from greater than 7 to 10, from 8 to 14, from 10 to 14, from 7.5 to 13.5, or from 8 to 13). In some examples, the methods further comprise collecting the produced hydrogen and optionally storing the produced hydrogen. In some examples, the methods further comprise collecting the solubilized iron, solubilized mineral-hosted catalyst, the intermediary catalyst-iron-compound, and / or aqueous catalyst, and optionally recycling them to repeat any of the methods described herein. In some examples, the methods further comprise collecting the solubilized iron, solubilized mineral-hosted catalyst, and / or aqueous catalyst, and optionally recycling them to repeat any of the methods described herein. In some examples, the methods do not produce a significant amount of greenhouse gases, such as CO2and CH4. In some examples, the methods do not produce a significant amount of CO2. For example, the methods produce 1 kilogram or less of CO2equivalent (CO2eq) per kilogram of produced H2 (e.g., 0.9 kg CO2eq / kg H2 or less, 0.8 kg CO2eq / kg H2 or less, 0.7 kg CO2eq / kg H2 or less, 0.6 kg CO2eq / kg H2 or less, 0.5 kg CO2eq / kg H2 or less, 0.45 kg CO2eq / kg H2 or less, 0.4 kg CO2eq / kg H2 or less, 0.35 kg CO2eq / kg H2 or less, 0.3 kg CO2eq / kg H2 or less, 0.25 kg CO2eq / kg H2 or less, 0.2 kg CO2eq / kg H2 or less, 0.175 kg CO2eq / kg H2 or less, 0.15 kg CO2eq / kg H2 or less, 0.125 kg CO2eq / kg H2 or less, 0.1 kg CO2eq / kg H2 or less, 0.090 kg CO2eq / kg H2 or less, 0.08 kg CO2eq / kg H2 or less, 0.07 kg CO2eq / kg H2 or less, 0.06 kg CO2eq / kg H2 or less, 0.05 kg CO2eq / kg H2or less, 0.045 kg CO2eq / kg H2or less, 0.04 kg CO2eq / kg H2or less, 0.035 kg CO2eq / kg H2or less, 0.03 kg CO2eq / kg H2or less, 0.025 kg CO2eq / kg H2or less, 0.02 kg CO2eq / kg H2or less, 0.015 kg CO2eq / kg H2or less, 0.01 kg CO2eq / kg H2or less, 0.005 kg CO2eq / kg H2or less, or 0.001 kg CO2eq / kg H2or less). In some examples, the methods produce 0.001 kilograms or less of CO2equivalent (CO2eq) per kilogram of produced H2. In some examples, the methods produce substantially 0 kilograms of CO2 equivalent (CO2eq) per kilogram of produced H2. In some examples, the methods are economical. For example, the methods can maintain costs to (one US dollar) $1 per kilogram (kg) of produced hydrogen or less (e.g., $0.9 per kg of produced H2 or less, $0.8 per kg of produced H2 or less, $0.7 per kg of produced H2 or less, $0.6 per kg of produced H2 or less, $0.5 per kg of produced H2 or less, or $0.4 per kg of produced H2 or less). Also disclosed herein are methods of use of hydrogen produced by any of the methods described herein. For example, the methods can comprise using the produced hydrogen for energy production and / or industrial purposes. In some examples, the methods can comprise using the produced hydrogen for energy production, energy carrier and fuel, energy storage, and / or industrial purposes, including as industrial feedstock, such as, but not limited to, ammonia, methanol, petroleum refining, metallurgy, electronics and glass manufacturing. A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims. The examples below are intended to further illustrate certain aspects of the devices and methods described herein, and are not intended to limit the scope of the claims. EXAMPLES The following examples are set forth below to illustrate the methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present invention which are apparent to one skilled in the art. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of measurement conditions, e.g., component concentrations, temperatures, pressures and other measurement ranges and conditions that can be used to optimize the described process. Example 1 – Catalyst-enhanced hydrogen generation from iron-bearing rocks Described herein is the use of element catalysts that may be natural mineral-hosted elements and / or applied aqueous catalysts (including applied solid catalysts that can be solubilized) that are used to increase rates of hydrogen production and lower temperatures of reaction necessary to produce hydrogen in rocks. Applied aqueous catalysts can increase the rate of hydrogen production by: 1) activating the chemical reaction between hydrogen in water and iron, which may be either chemically bonded in minerals in the rock or in aqueous phase, and 2) increasing the dissolution rates and solubility of iron (Fe2+) in rocks. The rocks may be subsurface (i.e., below the ground level), or on the surface (ex-situ). The produced catalyst- enhanced reactions include mineral reactions that involve the oxidation of iron (Fe+2to Fe+3) to generate hydrogen through the reduction of water and / or minerals or compounds that contain hydrogen. Examples of catalysts include, but are not limited to, transition metals, such as nickel (Ni) and copper (Cu), and platinum group elements, such as platinum and palladium. Catalyst compounds include associated halogen compounds used to increase the solubility of iron in solution. The compositions and methods described herein can produce hydrogen from rocks and associated fluids so that it can be stored and pumped to be utilized for energy production, energy storage, and / or industrial purposes. The operation can include subsurface and surface utilization of element catalysts. Utilization of element catalysts to enhance the production of hydrogen from mineral and rock reactions is unique. A key approach to this technology is the use of catalysts and their associated halogen compounds to increase the solubility of iron in solution and decrease the temperatures of reaction to form hydrogen. The application of element catalysts to iron-containing rocks for the purpose of producing hydrogen solves the problem of the relatively high temperatures of reaction that are necessary to produce hydrogen from iron-bearing rocks. By lowering the temperature of reaction necessary to form hydrogen, this process can increase the yield of hydrogen production in rocks, make more shallow rocks (residing at lower temperature and pressure) within the uppermost part of the crust available for hydrogen production, and decrease the amount of energy necessary to produce hydrogen. Further, the technology represents a new energy resource potential that can be harnessed outside of oil and gas basis, and potential to capture CO2. Current technologies to engineer the production of hydrogen do not exist. The closest analog to this process is the natural process called ‘serpentinization’ which occurs in ultramafic rocks whereby Fe+2in olivine and pyroxene are reacted to form minerals with Fe+3(oxidation) that is coupled to chemical reduction of hydrogen in H2O to H2. Low temperature formation of hydrogen. The technology herein works on a wide range of Fe-bearing rocks, such as igneous, metamorphic, and sedimentary rocks; the technology herein is not limited specifically to mafic and ultramafic rocks. The process does two things: 1) increase the dissolution of Fe-bearing minerals to make the iron more reactive towards hydrogen generation, and 2) create secondary mineral phases that are integral to the oxidation of Fe+2to Fe+3. The hydrogen generation process is unique, and further it can be optionally combined with additional technologies including carbon mineralization and liberation of critical minerals from rocks. The combination of technologies (carbon mineralization, hydrogen production, and liberation of critical minerals from rocks) is unique. The critical minerals in the rocks that are used to catalyze hydrogen production can also be extracted from the subsurface (in the aqueous phase or in solid compounds produced through reaction). The availability of catalysts in contact with iron in minerals found in rocks may be limited. This can be overcome by forming aqueous solutions that contain iron in its reduced state (Fe+2) and / or element catalysts that facilitate reactions that produce hydrogen. If the catalyst does not exist in the rock, the catalyst has to be provided, representing an additional cost. This cost can be overcome because the catalysts can be recycled and used in multiple subsurface well applications. If the natural catalysts are immobile, there is additional cost to inject aqueous fluids to mobilize the catalysts (e.g., CO2). This cost can be overcome through CO2credits by sequestering and storing the injected CO2in mineral form (carbonate) within the rocks (through a process called carbon mineralization). Hydrogen producing reactions described herein can be coupled to reactions that consume carbon molecules and produce carbon-bearing minerals. For example, the methods can comprise injecting CO2 to generate an acid in situ that can solubilize iron in the rock. Example 2 H2 production currently depends on energy-intensive, high CO2-emission steam reforming methods to meet global demand; less than 0.7% of H2 production is sourced from low- CO2-emission sources, and >90% of global H2 is sourced from fossil fuels that yield 7.5-12 tons of CO2 per ton H2 produced. New low CO2-emission H2 resources are necessary to meet global H2demand that is projected to increase from 95 Mt H2(2022) to 200 Mt by 2030 for net zero emissions by 2050. Existing white-hydrogen resources are not at a sufficient scale to meet future global H2demand. For example, a natural H2well in Bourakebougou, Mali produces 98% H2and has gained considerable excitement about the potential for native H2resources, but with a production rate of 1500 m3 / day, it falls far short of defining a deposit with a potential of >1 million m3 / day H2. In fact, all known H2 natural seeps taken together, such as those in Oman, Turkey, New Caledonia, Philippines, and Kansas, are orders of magnitude away from providing the necessary H2 production rates. Described herein is an understudied, but potentially transformational, aqueous injection and mineral catalyst-enhanced reaction mechanism to overcome rate-limiting steps and reaction barriers for economical (<$1 / kg), low-T (<100°C), H2 production in Fe-rich rocks. The technology described herein applies element catalysts to: (1) optimize H2-producing reaction pathways, (2) overcome sluggish reaction activation energies, (3) employ excess heat from exothermic reactions to trigger reactions in the low-T shallow crust, and (4) utilize increased volume of reaction and associated geomechanical changes (reaction-driven cracking) for propagation of reaction through the rock matrix. This technology features element catalysts that may be natural mineral-hosted elements and applied aqueous catalysts that are used to increase rates of hydrogen production and lower temperatures of reaction necessary to produce hydrogen in rocks. The application of element catalysts to iron-containing rocks for the purpose of producing hydrogen solves the problem of the relatively high temperatures of reaction that are necessary to produce hydrogen from iron-bearing rocks. By lowering the temperature of reaction necessary to form hydrogen this process can increase the yield of hydrogen production in rocks and decrease the amount of energy necessary to produce hydrogen. The technology described herein may be of interest for mining and energy companies, green energy companies, chemical companies that produce hydrocarbons from hydrogen-bearing reactants, etc. Example 3 - Sustainable H2 Production From Abiotic Catalyst-Enhanced Stimulation Of Iron-Rich Rocks Hydrogen (H2) is produced naturally in the Earth’s crust in situ from hydration of Fe-rich rocks, but this natural process has yet to be harnessed as a global H2 resource. Although exploration efforts are underway to find economic H2 reservoirs (‘white-hydrogen’), deposits of white-hydrogen at a scale sufficient to meet current and future global H2 demands have yet to be found. Laboratory experiments and field studies demonstrate the capacity for Fe-rich rocks to produce H2in situ, but also show that reaction kinetics are slow and require elevated temperatures (T) >200°C for significant reaction progress [1–3]. Enhancing in-situ production of H2(orange-hydrogen) in Fe-rich shallow crustal (< 3 km) deposits offers an enormous opportunity to generate economical and low-carbon H2at the global scale given the geographic distribution and volume of Fe-rich shallow crustal rocks, but requires overcoming important geochemical challenges. The technology described here seeks to unlock economically viable, low-carbon orange hydrogen by applying mineral-hosted reaction catalysts in Fe-rich rocks. Reaction catalysts including nickel (Ni) and platinum group elements (PGE) are commonly used to overcome activation energies, increase reaction rates, and lower reaction T (Figure 1). Here, Ni- and PGE-rich, mineral-hosted catalysts in (ultra)mafic rocks can be utilized to drive H2- producing reactions at lower T. An understudied, but potentially transformational, aqueous injection and mineral catalyst-enhanced reaction mechanisms are investigated to overcome rate-limiting steps and reaction barriers for economical (<$1 / kg), low-T (<100°C), H2production in Fe-rich rocks. Three Fe-rich rocks are considered: 1) ultramafic peridotites, pyroxenites, and dunites including ultramafic rock-hosted, Ni-Co-PGE deposits, 2) mafic basalts, gabbros, and other (ultra)mafic- intermediate composition variants, including those associated with the Midcontinent Rift, and other intrusive and extrusive occurrences within the shallow crust, 3) Archaean banded iron formations that exist around the world. Benchtop experiments on samples from three well- characterized rock types serve to quantify reaction rates under different temperatures, fluid chemistries, mineralogic compositions, and catalyst-enhanced strategies. Reaction rates from experiments serve to inform reactive transport simulations to quantify field-scale H2 generation capacity for each rock type under different scenarios. Collectively, this research serves to: 1) quantify the amount of H2that can be produced from shallow subsurface ultramafic, mafic, and banded iron formation bodies, and 2) validate the increased efficiency in H2production using different catalyst strategies. H2production currently depends on energy-intensive, high CO2-emission steam reforming methods to meet global demand; less than 0.7% of H2 production is sourced from low- CO2-emission sources, and >90% of global H2 is sourced from fossil fuels that yield 7.5-12 tons of CO2 per ton H2 produced [4,5]. New low CO2-emission H2 resources are necessary to meet global H2 demand that is projected to increase from 95 Mt H2 (2022) to 200Mt by 2030 for net zero emissions by 2050 [6]. Existing white-hydrogen resources are not at a scale sufficient to meet future global H2 demand [7–9]. For example, a natural H2 well in Bourakebougou, Mali produces 98% H2and has gained considerable excitement about the potential for native H2resources, but with a production rate of 1500 m3 / day [8], it falls far short of the goal of defining a deposit with a potential of >1 million m3 / day H2. In fact, all known H2natural seeps taken together, such as those in Oman, Turkey, New Caledonia, Philippines, and Kansas, are orders of magnitude away from providing the necessary H2production rates to meet such goals [9–12]. Continued exploration for white-hydrogen deposits is important, but, unless considerable discoveries are made, H2 production will need to be supplemented with additional H2 resources. H2 forms naturally in the Earth’s crust through abiotic mineral reactions in Fe-rich rocks, but these reactions occur at relatively high T and P (depth) over geologic timeframes. Stimulating H2 production from Fe-rich rocks (i.e., orange-hydrogen

[0013] ) presents an enormous opportunity to bring the United States closer to net zero CO2 emissions by 2050. A primary challenge with utilizing Fe-rich rocks for H2generation is devising strategies that enhance and stimulate sluggish geochemical reactions to occur at low T while maintaining well-head costs to below $1 / kg H2and minimizing CO2production to less than 1 kg CO2eq / kg H2. For orange-hydrogen to achieve scale to meet global H2demands, several challenges must be addressed. Specifically, there remains a lack of understanding of fundamental questions including reaction pathways, how much H2can be generated realistically at low T, how reaction volume increases will affect rock mechanics, and how geoengineering strategies can accelerate reaction kinetics to enhance H2 production at low T. By meeting these challenges, subsurface Fe- rich rocks including ultramafic and mafic rocks and banded iron formations could be harnessed to produce economically viable H2 at low T. It is estimated that there is a potential for H2 production in excess of 7000Gt in the United States. The key to unlocking low CO2-emission, sustainable orange-hydrogen is to lower the T of H2-generating reactions through low-cost catalysts. The state of the art for geoengineered orange-hydrogen does not exist in the global marketplace, representing an un-utilized resource waiting to be tapped. Herein, the state of the art of orange-hydrogen is described in terms of: 1) serpentinite H2-producing reactions observed in field, experiment, and thermodynamic modeling, and 2) chemical engineered catalysts that enhance H2-producing reactions. Serpentinization of olivine (Olv) in ultramafic rocks occurs at T <400°C to form Mg-rich hydrous serpentine-group silicates (Srp), brucite (Brc), and magnetite (Mgt) [14–16]. Fluids associated with serpentinites are reduced (H2-rich), alkaline, generally high pH (pH>10), and low silica activity [3,17–19]. Fluid chemistry, T, Fe-Mg content, and water-rock ratios are controlling factors to H2 production [3,20,21]. Figure 2 illustrates serpentinization of Olv (MgSiO4) and water (H2O) to form Brc (Mg(OH)2) and Srp (Mg3Si2O5(OH4)) with an extended compositional space that includes FeO and Fe2O3for Mgt (Fe3O4) formation [3]: 2 (Mg,Fe2+)2SiO4+3H2O = (Mg,Fe2+,3+)3(Si,Fe3+)2O5(OH)4+(Mg,Fe2+)(OH)2+(Fe2+,3+)3O4+H2 Enhancing reactions that form Fe3+products is important for H2generation. Thermodynamic modeling predicts Mgt stability in Fe-rich peridotites at T between 100-300°C, and Brc and Srp stability in the absence of Mgt at T < 100°C, potentially limiting H2 production in low-T reactions [3]. However, FeMg-1 exchange at T < 200°C favors formation of Fe-brucite

[0022] . Enhancing secondary oxidation reactions of Fe-brucite is an alternative reaction pathway to form H2

[0022] . A third reaction pathway towards low-T H2 generation is observed in the Mid- Atlantic Ridge – Kane transform fault (MARK), where late-stage low T (< 200°C) and high water-rock ratio Srp growth without Mgt includes Fe3+enrichment in Srp (cronstedtite) with H2 production [2,21,23,24]. Beyond serpentinization, chemical engineering studies use catalysts to enhance H2production. Ni2+-promoted H2production from Fe(OH)2decomposition at 50-90°C (pH = 11.5) show faster kinetics from the catalytic role of Ni2+to reduce H2O

[0025] . A recent advance in Ni- Fe and Co-Fe (oxy)hydroxides catalysts outlines a strategy to propel large-scale H2production in alkaline solutions. Enhanced H2-generation in alkaline media with Ni-Fe and Co-Fe (oxy)hydroxides with high-valent transition metal addition increased reaction rates by one order of magnitude

[0026] . Thus, ultramafic rocks with mineral-hosted Ni, Co and transition metals (W, Mo, Nb, Ta, Re) catalysts are promising in that they may sustain high H2-production rates at low T. The technology described herein applies mineral-hosted catalysts intrinsic to ultramafic rocks such as Ni and PGE in olivine and accessory phases (awaruite and heazlewoodite) to: (1) optimize H2-producing reaction pathways, (2) overcome sluggish reaction activation energies, (3) employ excess heat from exothermic reactions to trigger reactions in the low-T shallow crust, and (4) utilize increased volume of reaction and associated geomechanical changes (reaction- driven cracking) for propagation of reaction through the rock matrix. This technology specifically targets chemical oxidation of Fe2+to Fe3+coupled to water reduction to form H2 in Fe-rich rocks

[0027] . Investigated rock types include: 1) ultramafic dunites (>90% olivine) and peridotites (olivine and pyroxene mineralogy), 2) basalts (pyroxene and plagioclase mineralogy with trace olivine) including alkali basalts, and 3) banded iron formations (BIF). Unique to this technology is the focus on mineral-hosted catalysts that will ultimately lower H2 production costs. Multiple reaction pathways are pursued. Two specific paths include: 1) a primary reaction of olivine and pyroxene Fe2+oxidation to Fe3+-rich serpentine minerals (cronstedtite) and / or magnetite, and 2) a secondary reaction promoting oxidation of ferroan brucite ((Mg,Fe)OH2) to produce H2. Current results demonstrate enhanced H2generation from Fe(OH)2decomposition to magnetite (Fe3O4) with the presence of Ni2+catalyst at 90°C. H2yield is 50 times greater with a weak-base pH compared to strong-base conditions when the [Fe2+] / [Ni2+] ratio is 20:1 in aqueous solution (Figure 3). A second reaction conducted illustrates the formation of H2 and Fe-brucite in the absence of magnetite at 90°C, consistent with results from the Samail Ophiolite

[0028] . Based on these results, it is proposed to expand the reaction matrix with a suite of catalyst-enhanced experiments at different T, fluid chemistries, mineralogies, and catalyst-strategies using ultramafic, mafic, and BIF samples to: 1) optimize low-T primary reactions that produce cronstedtite from olivine and pyroxene Fe-Mg solid solutions, and 2) optimize secondary reactions focused on oxidation of ferroan brucite to magnetite and / or ferric iron hydroxides. Cumulative H2generation potential. Given the distribution of mafic and ultramafic rocks and BIF within the shallow crust (<3 km) of the United States [29,30] broad impact is ensured. The technology described here to enhance H2production may exceed technical performance goals of >10Mt H2 deposit potential and >1 million m3H2 / day deposit production rates. Estimates of H2 production from serpentinization vary considerably; slow mid-ocean ridge spreading centers yield an estimated 0.5–2.0 kg-H2 / m3-for peridotite between 200-350°C

[0031] . Using these production estimates a cumulative estimate of H2-generation potential in the US exceeds 7000 Gt: • United States ultramafic bodies – West coast (California (CA), Oregon (OR), Washington (WA)), east coast (North Carolina (NC), Connecticut (CT), Massachusetts (MA), Vermont (VT), and New York (NY)), and Interior (Missouri (MO), Minnesota (MN), Wisconsin (WI), and Michigan (MI)) ultramafic rocks cover 16,263 km2

[0030] presenting a cumulative H2generation potential of 350 Gt H2. • Columbia River Basalts – An area of approximately 164,000 km2across Oregon (OR), Washington (WA), and Idaho (ID) in the Pacific Northwest is covered with 4 km of mafic basalts that have an average FeO content of 10%, presenting a cumulative H2 generation potential of 5,150 Gt H2. • Midcontinent Rift – Distributed across parts of Michigan (MI), Wisconsin (WI), Minnesota (MN), Iowa (IA), Kansas (KS), and Nebraska (NE), the Midcontinent Rift covers a 100,000 km2area with 1-4 km of Fe-rich (10-12% FeO) mafic basalts, presenting a cumulative H2 generation potential of 1,800Gt H2. • Banded Iron Formation – primarily in Wyoming (WY), Missouri (MO), and Michigan (MI). Unknown potential, estimates from Atlantic City Mine, Wyoming alone are 30Mt H2. Advancing science for the optimization of under-utilized rocks. This technology serves to increase knowledge of H2-generating reactions and unlock a renewable source of H2that could replace hydrocarbons with a clean, carbon-free energy. This technology could transform the mining industry supply of critical minerals, and create a pathway to large-scale, and affordable methods to lower greenhouse gas emissions, increase mining efficiency, and decrease costs. Challenges in finding adequate, low-cost in-situ catalysts that allow utilizing Fe-rich rocks to generate viable geologic H2 are met through integration of various tasks outlined here that includes detailed rock characterization and representative rock selection (Task 1), benchtop experiments to quantify reaction kinetics on representative samples (Task 2), understanding the behavior of mineral-hosted reaction catalysts (Task 3), and meso- and subsurface-scale geomechanics (Task 4) Three field sites are described here. The first site is an ultramafic rock-hosted, Ni-Co- PGE deposit that is a shallow 45 km2body of dunite, peridotite (and serpentinized equivalents), and lesser pyroxenite and gabbro (Figure 4). Here, petrologic and geochemical assessments from other studies are built upon and mineralogy and distribution of Fe- and Ni-rich minerals (awaruite, heazlewoodite, pyrrhotite, magnetite, Fe-serpentinite) throughout the deposit are focused on as mineral-hosted catalysts and minerals available for reaction within these rocks are investigated. The second study site includes basaltic rocks of the Midcontinent Rift System (MRS) in the Central Iowa Horst

[0032] (Figure 4, panel A). The volcanics are graben-filled mafic- dominated bimodal volcanics, with an estimated 106km3volume

[0033] . Obtained subsurface cores preserve 14 m of amygdaloidal basalt and 21 m of gabbro. The deepest MRS intervals include 45 m of unaltered gabbro drill cuttings collected from 5,395 to 5,441 m depth, all of which are made available for this work. The third study site includes BIFs within the Atlantic City Mine, Wyoming. The Atlantic City Mine BIF includes 20-40’ thick quartz-rich bedded chert with abundant Fe-rich magnetite and amphibole (gruenerite), which are the target minerals for this study

[0034] . Although magnetite contains substantial proportions of Fe3+, total Fe content of up to 42% (average = 30%) within BIF supports this rock type as a potentially important target for H2production. Task 1: Rock characterization and representative rock type selection. Petrologic, geochemical, and geomechanical characterization of rocks (cores, core plugs, and rock chips) across the three field sites serve to identify representative rock samples for reaction kinetics experiments outlined in Tasks 2 and 3. Existing geochemical datasets are leveraged. Analysis of reaction products from Tasks 2 and 3 is included here. Subtask 1.1. Advanced geochemical characterization. Characterization data gaps are complimented with new analyses including Wavelength Dispersive X-ray fluorescence (WD- XRF), Automated mineralogy system (AMICS) for scanning electron microscopy (SEM), electron microprobe analysis (EPM), Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS), X-ray diffraction mineralogy (XRD), Raman spectroscopy, and Mössbauer spectroscopy. Evaluating Fe2+content for reaction is key. Subtask 1.2. Representative rock selection. Synthesis of all data (Subtask 1.1) serve to define representative suite of rocks for experiments. Rock types are categorized with consideration to their H2 generation potential. Task 2: Benchtop experiments to evaluate reaction kinetics in rocks. Reaction experiments that include: 1) no injected aqueous catalysts, and 2) catalyst-enhanced reactions to identify rate-limiting reaction steps and H2 yield potential with respect to T, water-rock ratio, Fe- abundance, mineral-catalyst host, and aqueous chemistry for selected rocks (Task 1). Each reactor (Subtask 2.1-2.5) is demonstrated inert to H2reaction and diffusion at their respective T range. Reaction progress is monitored through time-series fluid / gas chemistry sampling, and reaction products evaluated with a combination of analytical tools (Subtask 1.1). Subtask 2.1. Low-T batch reactor. Mineral-gas-liquid experiments conducted in 65 ml septum-sealed serum bottles up to 90°C. H2reaction yield sensitivity to T, pH, alkalinity, salinity, mineral chemistry, and fluid-rock ratios are explored and monitored through time series gas-liquid sampling, and solid-mineral analysis at the end of the experiment (Subtask 1.1). Subtask 2.2. Autoclave batch reactor. Stainless steel stirred reactor for larger scale (150 ml aqueous volume and 10 g rock) at elevated T and pressures (P) (up to 200°C and 500 bars) to validate reaction mechanisms at a range of reservoir conditions. Subtask 2.3. High-T and P rocker-bomb experiments. Limited set of batch hydrothermal rocker-bomb experiments to validate fluid-rock reactions and extend experimental reaction mechanisms to high T and P (up to 500°C and 3 kbar) [35,36]. Time series gas-liquid samples are analyzed through the experiment, and solid mineral characterization at experiment conclusion to validate reaction mechanisms. Subtask 2.4. Core-flood reactor. Core plugs and packed mineral reactors to validate reactive transport at reservoir conditions. Time-series fluid samples are analyzed to provide insight into dynamic water-rock interactions. Permeability shifts in core and packed mediums are evaluated. Precise P measurements serve to identify even subtle permeability changes from fracture generation or sealing. Subtask 2.5. Real-time fluid inclusion micro-reactor imaging. Olivine and pyroxene hydration reactions are observed in-situ through synthetic fluid inclusions in minerals coupled to an optical microscope-mounted heating stage [37,38]. Generated inclusions in pre-fractured crystals are loaded into platinum capsules with controlled aqueous solutions (i.e., salinity, pH, alkalinity) using cold-seal pressure vessels. Reaction between inclusion fluid and host crystal to create serpentine and brucite, along with magnetite and H2gas is viewed optically [37,39]. Final fluid compositions (aqueous solutions, H2) examined by microthermometry, Raman spectroscopy and extraction in a vacuum chamber connected to GC-MS system. Task 3: Experimental validation of catalyst-enhanced reaction kinetics. Enhanced mineral reaction experiments (i.e., injection of aqueous catalysts, and pre-conditioning of mineral-hosted catalyst) are studied to maximize H2 yield from mineral reaction. Pure-phase single-mineral catalyst experiments are followed with more complex rock types to quantify reaction rates for H2 generation and validate catalyst-enhanced reaction mechanisms across rock types selected in Task 1 and tested in Task 2. Potential catalyst poisonings are identified. Reaction rates are quantified for 1) in-situ mineral-hosted catalysts, 2) injected aqueous-based catalysts, and 3) coupled reactions (primary and secondary) used to optimize and pre-condition mineral assemblages, and evaluate sensitivity to water-rock ratios, aqueous chemistry, and pH. Subtask 3.1. Aqueous catalysts – injected solutions. Aqueous catalyst experiments following experimental methods and results from Tongwei Zhang that monitored H2generation from mineral dissolution in the presence of Ni2+catalyst. Optimal aqueous conditions under natural mineral buffers (T, pH, alkalinity, and catalyst concentration) are explored to enhance H2 production. Transition metal chloride solutions (i.e., NiCl2, CoCl2, MoCl2) are evaluated. Results serve to inform aqueous-catalyst subsurface strategies that can be further evaluated in core-flood experiments (Subtask 2.4). Subtask 3.2. Pre-conditioned mineral-hosted catalyst. Experiment with strategies to pre- condition mineral-hosted catalysts to optimize catalyst availability for subsequent H2-generating reactions. In the Ni-Co-PGE ultramafic ore deposit, transition group elements are primarily hosted in olivine in unaltered (unserpentinized) rocks and in awaruite, heazlewoodite, pyrrhotite, magnetite, and serpentinite where altered. Mineral-hosted catalyst solubility, solution alkalinity and pH, and grain size are potential reaction-rate limiting factors that are evaluated through experiment. Reaction rates for H2 generation are measured at various T. Transition metal catalytic effects might be poisoned from mineral reactive surface coatings or reaction of available transition metals to non-reactive mineral products. These effects are investigated by adjusting aqueous chemistries. Task 4. Geomechanical rock property experiments. Meso-scale pore-P effects and reaction-driven cracking associated with H2-producing mineralogic reaction are explored. Subtask 4.1. Meso-scale (core-plug) geomechanical experiments. Representative suites of rocks (cylindrical rock plugs) down-selected from Task 1 using high-T, high-P triaxial machines (GCTS RTR-1500 and NER Autolab 3000) at reservoir conditions using pore-fluid reactive chemistries identified in Task 3. Radial and axial deformations are measured to determine reaction-driven volumetric changes and potential cracking. Acoustic emissions serve to determine rock fracture and crack stress thresholds during pore-fluid P buildup. Measured stress- strain responses under the axial loading stage are used to determine the elastic properties of rocks from the three sites. Rock mineral characterization results from Task 1 are utilized to understand the changes in geomechanical behaviors, such as crack propagation and brittle- ductile failure. Techno-economic analysis. Most of today’s H2 is produced by reacting methane with steam at high P (gray-hydrogen) which results in 900 MtCO2 emitted every year

[0042] . A more climate friendly process is to produce H2by splitting water molecules with electrolyzers using renewable solar or wind power (green-hydrogen). The cost to produce gray-hydrogen is typically in line with the price of natural gas (~$2.5 / kg), whereas green-hydrogen costs twice as much. For natural H2to compete with relatively inexpensive hydrocarbons, the cost per kg needs to drop to <$2 / kg, preferably <$1 / kg which would allow it to dominate the market. The main expenses are 1) the injection of fluids into the rock at high P, which require power, and 2) costs associated with catalysts. This technology focuses on exploiting catalysts that are already present in the rocks to minimize costs, so the goal of reaching <$1 / kg using intrinsic catalysts seems very achievable. At the beginning of the operation, electricity would come from renewable sources, but once H2 is produced from the rocks it would be used to power fluid injection, further lowering the costs of the overall operation. Once the catalyst-enhanced H2-generation technology is proven to work in the laboratory, the technology is tested in the field through an in-situ fluid injection into a reactive, Fe-rich rock body, preferably a Ni-rich ultramafic formation, Tamarack mine (Minnesota (MN)), or Eagle mine (Michigan (MI)) (Figure 4, panel A). Background H2levels are measured downhole prior to fluid injection. Following a stable background reading, reactive Fe-rich rocks are injected with an un-enhanced fluid (i.e., pure water) for 1-4 week(s) and H2 levels are measured after the injection using monitoring wells around the injection site. Following a pure- water injection, injection fluid are optimized to trigger maximum, safe (minimizing risks) H2 generation from specific rocks and after a similar 1-4 week injection H2 levels are measured. If the enhanced methodology triggers a H2 production rate increase from 5x104kg / sec (serpentinization) to 5x109kg / sec (mineral-hosted catalyst reaction), the technology is deemed successful and ready for upscaling. Upscaling entails conducting longer injections using multiple wells within a single rock body, as well as conducting similar tests followed by upscaled injections in different rock types (i.e., basalts, BIF). The market for this technology is companies or countries (governments) that have access to Fe-rich rocks and would like to incorporate geologic H2into their operations and economies, for example, as an alternative to natural gas. Mining companies especially could benefit from having a clean energy source beneath their feet that could not only power the mining operation but could potentially generate a surplus of H2 to be sold for profit. Mining companies that target critical metals that can act as catalysts for H2 generation are of high interest due to the low cost of the technology arising from the intrinsic presence of catalysts in the rocks. In the USA, viable rock formations exist in the western and eastern states as well as along the Midcontinent Rift System (Figure 4). Although, compared to ultramafic rocks, mafic rocks such as basalts contain less Fe (~10 wt% in ultramafics compared to 8 wt% in mafics) and less critical metals, volumetrically they expand far larger areas in the shallow crust (<3 km) and are thus also desirable places for the application of this technology. The viability of other Fe-rich rocks such as BIF is to be determined from this study. In conclusion, most countries, including the oceans, contain rocks where this technology could be applied so the potential for upscaling is tremendous. One of the potential limiting factors for the applicability of the technology is the availability of water near the rocks to be geostimulated to produce H2. Many of the (ultra)mafic bodies where the technology could be applied are in or near oceans, which offer a source of saline water (see Carbfix Atlas for distribution of shallow mafic-ultramafic rocks). The feasibility and risks associated with using saline versus freshwater is evaluated in Tasks 2 and 3. Another potential limiting factor is the low permeability of ultramafic rocks, which may limit the ability of fluids to penetrate and react with fresh rock, as well as limited reactivity at low T. An up to 30% volume increase may occur as a result of geoengineered serpentinization and an intrinsic source of heat produced by exothermic reactions. The effects of these reactions on permeability and rock reactivity is evaluated in Tasks 2, 3, and 4. Finally, the availability of low- cost catalysts may be a limiting factor. In Task 3, a focus is on exploring low-cost catalysts, with special focus on metal catalysts naturally present in Fe-rich rocks. Despite the potential economic viability of the proposed technology, the reason why geoengineered in-situ H2 production like the one proposed here is not being pursued by industry today is because the realization of the potential for in-situ generation from relatively shallow rocks is recent, and because processes are not well understood. This project can help to shed light on essential H2-generating reactions as well as finding ways to accelerate naturally occurring processes to unlock a renewable, controllable, source of H2that could be exploited in a similar way to hydrocarbon reservoirs, but that unlike the latter, offers a clean, carbon-free, and renewable source of energy. 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A compilation of rate parameters of water- mineral interaction kinetics for application to geochemical modeling. USGS Open File Report vols 2004–1068 (2004). 42. Hand, E. Science (80-. ).379, (2023). Example 4 – In-situ hydrogen production: geo-engineered serpentinization What are serpentinites? Hydrated ultramafic (Mg-rich) rocks that formed near mid- ocean spreading centers that produce hydrogen (Figure 1, left panel). What is serpentinization? Metamorphic hydration of ultramafic rocks (olivine-rich) by seawater at slow and ultra-slow-spreading mid-ocean ridges (following equation and Figure 5) 2 Olivine (Fe2+) + 3H2O = Brucite + Serpentine + Magnetite(Fe3+) + H2 The geographic distribution of modern serpentinization is described by Guillot and Hattori (Elements, 2013, 9(2), 95-98). Objective of geo-engineering serpentinites: • Access a portion of the estimated 12,500 Gt (146 Gt in US) of H2 that can be produced from global iron reserves* (*extractable reserves from surface mining across all rock types) • Estimates as high as 150,000 Gt • 1 Gt of H2can power the US for 1yr • Current US H2consumption is 100 Mt / yr (1460 yr supply) • Utilize in situ reactive catalysts to increase H2yield and stimulate sluggish reaction kinetics at low temperature • Unlock clean H2production to replace CO2-intensive H2sources (i.e., steam methane reformation without carbon storage) Challenges of geo-engineering serpentinites: • High temperatures of reaction (kinetics) • Serpentinization occurs between 150-400°C • Ultramafic rocks have very low permeability (crystalline / fractured) • Locations are not ideal • Serpentinization is mostly associated with mid-ocean ridges • Hydrogen is highly reactive • Energy source for microbial activity and can reduce common mineral phases • Rare occurrences in reservoirs • Bourakebougou, Mali produces 98% H2 at 1500 m3 / day • Goal is > 1 million m3 / day Estimating H2 production from Fe-rich rock (3 km depth): - Include shallow crust (3 km) and the numbers are enormous (~150,000 Gt) - Ultramafic peridotite (> 90% olivine; 7.5% FeO) o 1km3deposit: 7 Gt H2o Coverage: 16,263 km2o Total H2: 338 Gt - Columbia River flood basalts (25-75% pyroxene; 12% FeO) o 1km3deposit: 11.2 Gt H2o Coverage: 163,700 km2o Total H2: 5150 Gt - Banded Iron Formations (magnetite; 30% FeO) o 60% global iron reserves o 1km3deposit: 27.8 Gt H2 o Atlantic City Mine ^ Coverage: 10 km2(100 m thick) ^ Total H2: 30 Mt ^ *1 / 3 of US H2consumption Engineering the Hydrogen out of the rocks. A schematic diagram of the technology described herein for engineering the hydrogen out of the rocks is shown in Figure 1 (right panel). Hydration of olivine and oxidation of Fe2+occurs as shown in Figure 2 and Figure 6. Table 1 summarizes the properties of various minerals. Enhancing Fe3+forming reactions can benefit hydrogen production according to Scheme 1. Table 1. Properties of various minerals. Scheme 1. Oxidation of Fe2+. Thermodynamic phase equilibria. Thermodynamic phase equilibria diagrams are described elsewhere (Klein F et al. Lithos, 2013, 178, 55-69) and indicate: magnetite is stable above 200°C; Serpentine and brucite at low T; Iron-rich minerals (Fo70vs. Fo90). Hydration of pyroxenites. Hydration of pyroxenites is shown schematically in Figure 7; relevant thermodynamic phase equilibria diagrams are described elsewhere (Klein F et al. Lithos, 2013, 178, 55-69). H2 generated from peridotites and pyroxenites. Thermodynamic phase equilibria diagrams are described elsewhere (Klein F et al. Lithos, 2013, 178, 55-69) and indicate peridotites produce an order of magnitude more H2 than peridotites at T, though reaction kinetics were not considered. For example, 1 kg of olivine can produce 325 mmol H2. Quantitative Fe2oxidation can produce 1300 mmol H2, though not all Fe2+oxidizes. Controlling factors. Controlling factors on H2 generation include, but are not limited to: - Mineralogy: Peridotites make more H2at lower temperatures - SiO2activity: Low SiO2activity favors H2- pH and alkalinity: high pH and alkalinity favors H2- mineral products: magnetite and FeIIIserpentine - Temperature: High temperature favors magnetite – FeIII(magnetite formation) Mineral-hosted nickel and platinum group element (PGE) ultramafic rocks can catalyze H2-producing reactions at lower temperature. For example, olivine in ultramafics have 1000 ppm to 1% Ni-enrichment, and accessory phases include awaruite (75% Ni), heazlewoodite (73%), and pentlandite (35%) (Kierczak J et al., Science of the Total Environment, 2021, 755, 142620). A goal of this work is to reduce the temperatures of reaction to <100°C with mineral-hosted catalysts. Batch experiments have been performed in peridotites (range of FeMg-1values in olivine). Parameters include adjusting mineralogy, water rock ratios, and alkalinity. Experiments also include catalyst-enhanced reactions (mineral hosted and aqueous). Results of the experiments were that detectable H2 was produced from an olivine and alkaline solution in less than 1 week. A ‘brucite gel’ was observed over the olivine grains. A comparison of batch experiments with actual ultramafics and thermodynamics was performed. The batch experiments are forming brucite, (Mg,Fe2+)(OH)2. H2 was detectable in the headspace, which suggested Fe2+is being oxidized to Fe3+. It is suggested that the experiments are forming cronstedtite (Fe3+serpentine). Low temperatures favor FeMg-1substitution in brucite. Secondary low temperature reactions oxidizing brucite to magnetite or Ferric-Srp. Example 5 – Producing Hydrogen From Rocks The technology described herein explores a suite of natural catalysts to help produce hydrogen gas from iron-rich rocks without emitting carbon dioxide. The project could jump-start a new type of hydrogen industry: geologic hydrogen. The technology described herein is a type of non-fossil fuel production of hydrogen from iron-rich rocks that has never been attempted at an industrial scale. The research explores the feasibility of this process on different rock types across the United States. Hydrogen is an important player in the energy transition because it does not produce CO2gas emissions when it is burned for fuel. Its only byproduct is water. However, most hydrogen gas today is produced from natural gas in a process that also produces CO2. Producing geologic hydrogen from iron-rich rocks would offer a major shift in the energy transition because of its low-carbon emission footprint. Replacing hydrogen that is sourced from fossil fuels with hydrogen sourced from iron- rich rocks has many benefits. The catalysts can stimulate a natural geologic process called “serpentinization.” During serpentinization, iron-rich rocks release hydrogen as a byproduct of chemical reactions. Serpentinization usually occurs at high temperatures. With natural catalysts that include nickel and other platinum group elements, the technology described herein can stimulate hydrogen production at lower temperatures and at depths easily accessible by today’s technology where iron-rich rocks are found throughout the world. That means catalyst-enhanced production of hydrogen from iron-rich rocks has the potential to significantly increase hydrogen production globally. Natural accumulations of geologic hydrogen are being found all over the world, but in most cases they are small and not economical, although exploration continues. The work described herein can generate larger volumes of hydrogen from these rocks by driving reactions that would take several million years to happen in nature. Successful tests have already been conducted at the laboratory scale. The experiments can be scaled up and the process can be tested on a broad range of iron-rich rock types found across North America. The use of the catalysts on basalts, banded iron formations in Wyoming and ultramafic rocks in the Midwest are investigated. Example 6 Data was collected for added catalysts (e.g., aqueous catalysts including Nickel and Vanadium) and natural catalysts (e.g., Nickel Sulfide). Additional information is provided in Example 7. Reactions were catalyzed using Ni, Co, Mo, and V, and the addition of these catalysts increases production rates of hydrogen. Graphs show increase of hydrogen production and data shows formation of Ni-Fe-OH compounds that are associated with hydrogen producing reactions. Therefore, in addition to acting as catalysts, some catalyst reactions are also working to form Fe-bearing compounds that promote the oxidation of Fe+2to Fe+3. Reactions are acting to mobilizing catalysts that are bound to other elements that are within rock minerals (i.e., nickel sulfide) can be mobilized into the aqueous phase to be available to reaction by adding additional chemicals (i.e., CO2). Results from high pressure reactions with basaltic rock compositions showed that rocks with more silica than ultramafic can be used to generate hydrogen. This demonstrates that iron- oxidation reactions are being utilized that are not limited to the typically described serpentinization reaction. This process combines multiple technologies (i.e., carbon mineralization and hydrogen production). With some rock types, it is possible to achieve similar results without addition of CO2. In ultramafic rocks there is a combined effect of carbon mineralization with hydrogen production that is enhanced through catalysts. This effect is also observed in mafic rocks. Catalysts can be recovered from the aqueous phase after they have been utilized to produce hydrogen. In addition, some of the solid compounds produced (Ni-Fe) are potential products that can be obtained from the subsurface. Figure 13 shows catalysts added to San Carlos olivine increase hydrogen production. Example 7 Catalyst-enhanced reactions were performed and enhanced H2generation using catalysts was validated. Increased H2-yield with catalyst-enhanced aqueous reactions on minerals was validated and quantified. The aqueous catalysts increased yield of produced hydrogen when applied to iron-bearing mineral phases compared to reactions without aqueous catalysts. Summary: Increased hydrogen yield through the use on Nickel catalysts on rocks was demonstrated using three independent means: 1) serum bottle reactions with aqueous solutions of nickel chloride (NiCl2 aq), nickel sulfide (NiS solid), and Vanadium Chloride (VCl3aq) with Fe+2Cl 2) high pressure (150 psi) Parr Reactor experiments with an alkali basalt from Uvalde, Texas 3) Low pressure – low temperature glass serum bottle experiments using ultramafic rocks, pure San Carlos olivine grains, and an alkali basalt from Uvalde, Texas Section 1: Serum bottle reactions with aqueous solutions. Results from three different aqueous catalyst experiments are described here. The NiCl experiments are shown here for comparison to demonstrate the effectiveness of NiCl catalyst to increase hydrogen yield. NiCl2: Experiments at 90°C demonstrate Ni catalyst to form H2 from Fe2+oxidation is significant. Figure 8 shows [Fe2+] / [Ni2+] ratios varied from 10 to 100, and H2 yield is 60 to 170 times higher than that without the presence of Ni catalyst. About 17 times larger H2 yields remains at [Fe2+] / [Ni2+] ratio as large as 160. The optimum range of [Fe2+] / [Ni2+] concentration ratio for H2generation is from 45 to 100. The following deductions can be made based on the experimental observations: 1) (Fe,Ni) (OH)2complex precipitation is required to catalyze hydrogen. Without NiCl2(Figure 8; square data point), the presence of Fe(OH)2precipitation and excess [Fe2+] in solution doesn’t show any increase of H2yield.2) high pH alkaline condition is required initially in order to form (Fe,Ni)(OH)2complex precipitation. In the presence of aqueous [Ni2+] and [Fe2+] under a weak acidic condition, H2 yield is low because (Fe,Ni) (OH)2 complex does not precipitate. Therefore, it is deduced that co-existence of [Ni2+] and [Fe2+] and precipitation of (Fe,Ni) (OH)2 complex at high pH alkaline condition could greatly enhance H2 generation from Fe2+oxidation. VCl3: A comparison of H2 generation from Fe2+oxidation with and without the presence of VCl3 was made at 90°C. These experiments build on the original NiCl2 experiments and are designed to evaluate additional catalysts and identify potential catalyst reaction pathways. Results show that H2yield in the presence of VCl3is very similar to the background value in the absence of VCl3at a wide range of pH conditions (7.12-11.7) (Figure 9). This comparison indicates that the VCl3does not play a role to catalyze H2generation from Fe2+oxidation. A reason might be attributed to the incompatible ionic radius and valence between V3+and Fe2+that inhibit the formation of reactive species of iron vanadium hydroxide complex. Nickel sulfide: Based on the success of the original aqueous Nickel Chloride (NiCl2) experiments, an additional source of Nickel, Nickel sulfide (NiS, solid), was explored. Nickel sulfide is a common mineral in ultramafic rocks and may act to catalyze hydrogen production in nature. A comparison of H2 generation from Fe2+oxidation in the presence of NiCl2 and NiS was made at 90°C. The results showed that H2yield in the presence of NiS (solid) is lower than that in the presence of NiCl2(aqueous) at a wide pH range of pH conditions (6.54-11.41), and is similar to the background value without NiCl2(Figure 10). This comparison indicates that the solid NiS does not play a role to catalyze H2generation from Fe2+oxidation. A reason is attributed to the insoluble behavior of NiS, resulting in extremely low Ni concentration in the solution. Addition of CO2 or other solubilizers would help dissolve NiS into the aqueous solution where it could act as a catalyst and probably have a similar effect to that of NiCl2 (aqueous). Conclusion of aqueous catalyst experiments: The aqueous catalyst experiments provide conclusive results that NiCl2 acts as a catalyst to increase the yield and rate of hydrogen gas in the presence of aqueous iron (Fe+2). The hypothesis is that an intermediary Fe+2Ni(OH) phase catalyzes the oxidation of Fe+2to Fe+3, subsequently forming Fe+3oxides (visible in the reactor) and H2gas (measured with gas chromatography). This NiCl2catalyst reaction is optimized at alkaline pH. The same observation was not made for vanadium chloride (VCl3), demonstrating the unique chemistry of transition metals, and likely the importance of for a Fe-transition metal complex. The Nickel sulfide experiment demonstrates the importance of solubility and reactivity of transition metal complexes: across a range of pH a catalytic effect between NiS(s) and aqueous Fe+2was not seen. The catalystic effect of NiS(s) may be greater in the presence of a solubilizer to make it NiS(aq). This is important because solid nickel sulfide and nickel iron sulfide compounds are common components of ultramafic rocks and also present in some mafic and even intermediate rocks. Being able to mobilize NiS into the aqueous solution using a solubilizer such as CO2 so that it can act as a catalyst would help reduce costs that associated with addition of an external aqueous catalyst. The positive NiCl results presented here are consistent with the results presented in the following two sections for rocks. Section 2: High pressure (150 psi) Parr Reactor experiments with an alkali basalt. A series of high pressure experiments were performed using two separate 160 mL Hastelloy steel high-pressure Parr® reactors with Teflon liners to investigate reactions with alkali basalts and nickel catalysts at reservoir pressure. Experimental conditions were as follows: 3.5 g crushed rock and 70 mL distilled water loaded into Parr reactors.0.03 M NiCl2was added to one reactor. Both reactors were pressurized with pure gas-phase CO2. To purge air and dissolved gases in the water a series of cycling between charging reactors to 150 psi, then evacuating under pressure were performed. Reactors were then heated to 90 °C to reach 150 psi pressure. Gas samples were measured after 21, 51 and 86 days for H2, N2, CO2, O2, and CH4 to measure changes in headspace gas composition, and quantify yield of hydrogen through reaction between rock, water, and NiCl2 catalyst. Gas chromatography results (Table 2 and Figure 11) clearly demonstrate: 1) increase in H2yield over time, and 2) that catalysts increased yield of produced hydrogen when applied to alkali basalts. Table 2. Comparison of H2concentration changes (in ppm) of the headspace of Parr reactors during experiments with Uvalde basalt (second column) and with NiCl2 addition (third column). Alkali basalt reaction pathway: Continued scanning electron microscopy, x-ray diffraction analysis, and aqueous geochemistry is being used to quantify reaction pathways. SEM images highlight the complex mineral reaction pathways that are occurring. Figure 12 illustrates pre-reaction and post-reaction (with CO2-saturated water) minerology changes, and highlights the effect these reactions can have on aqueous chemistry, and subsequent effect on catalyst behavior (i.e., complexation, pH, and alkalinity, and total dissolved solids). Alkali feldspar or feldspathoid dissolution can increase Na, K, Si, and Al aqueous concentrations, pyroxene dissolution can increase Mg, Fe, and Si aqueous concentrations, whereas chlorite and brucite precipitation can consume Mg, Si, Al, Fe, and Na. The effect of this changing aqueous chemistry is evaluated in the following section. Conclusion - High pressure Parr Reactor experiments with an alkali basalt: Parr reactor experiments have two important results: 1) NiCl2 effectively increases the yield of hydrogen for alkali basalts compared to rocks that are not treated with NiCl2, and 2) alkali basalts can produce hydrogen. The second conclusion expands the applicability of hydrogen production from ultramafic rocks to include mafic basaltic rocks. This significantly increases the range of possible geologic terranes where hydrogen production can be explored. Section 3: Low pressure – low temperature glass serum bottle experiments using ultramafic rocks, pure San Carlos olivine grains, and an alkali basalt Summary: 26 different experiments across 6 rock types (3 serpentinized ultramafic rocks, San Carlos Olivine and an alkali basalt), 2 gas saturations (argon and CO2), and 2 aqueous chemistries (deionized water and deionized water + nickel catalyst) were performed. The five rock types are described in Figure 15. Table 3 lists the measured results for the ultramafic, San Carlos, and alkali basalts. Figure 13 illustrates the effect that NiCl2 catalyst has on hydrogen production from olivine. Results have important conclusions for this study: 1) The mineralogy of the host rock (starting mineralogy) has significant effects on the amount of hydrogen that can be produced. Figure 15 shows that CAV-017 has the highest degree of serpentinization compared to San Carlos, CAV-005, and CAD-005, and subsequently yielded the lowest amount of hydrogen (see Figure 14). 2) Nickel Chloride (NiCl2) is an effective catalyst to increase the yield of hydrogen from iron-bearing rocks. Table 3 shows a doubling effect in the yield of hydrogen reported as mg H2 / m3rock in ultramafic rocks, and a 10x increase in San Carlos Olivine. Importantly, this is observed at low temperatures (75°C) and short time periods (100 days). Table 3. Experiment results of rock lithology, gas chemistry, catalyst, and hydrogen yield calculated as mg H2 / m3rock. Collective results: The results from three independent experiments validate the increased yield of hydrogen produced from ultramafic and mafic rocks. A factor of two- to ten- was observed at a temperature of 75°C during a time duration of 100 days. Additional aqueous geochemistry, X-ray diffraction for mineralogy, and scanning electron microscopy is being integrated to track reaction pathways and better understand the role catalysts play in the reaction(s) that form hydrogen. EXEMPLARY ASPECTS In view of the described compositions, devices, systems, and methods, herein below are described certain more particularly described aspects of the inventions. The particularly recited aspects should not, however, be interpreted to have any limiting effect on any different claims containing different or more general teachings described herein or that the “particular” aspects are somehow limited in some way other than the inherent meanings of the language and formulas literally used therein. Example 1: A method of enhanced hydrogen generation from iron-bearing rocks, the method comprising: contacting an iron-bearing rock with an aqueous solution comprising an iron solubilizer, a catalyst solubilizer, and / or a catalyst; wherein the iron solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of iron from the iron-bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen; wherein the catalyst solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron-bearing rock, when present, thereby increasing the availability of said mineral- hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; wherein the catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; thereby increasing the rate of hydrogen production and / or lowering the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said aqueous solution. Example 2: A method of enhanced hydrogen generation from iron-bearing rocks, the method comprising: contacting an iron-bearing rock with an iron solubilizer, a catalyst solubilizer, an intermediary catalyst-iron-compound, and / or a catalyst; wherein the iron solubilizer, when present, increases the dissolution rate and solubility of iron from the iron- bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen; wherein the catalyst solubilizer, when present, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron- bearing rock, when present, thereby increasing the availability of said mineral-hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; wherein the catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; thereby increasing the rate of hydrogen production and / or lowering the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said iron solubilizer, catalyst solubilizer, intermediary catalyst- iron-compound, and / or catalyst. Example 3: A method of enhanced hydrogen generation from iron-bearing rocks, the method comprising: contacting an iron-bearing rock with an aqueous solution comprising an iron solubilizer, a catalyst solubilizer, an intermediary catalyst-iron-compound, and / or a catalyst; wherein the iron solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of iron from the iron-bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen; wherein the catalyst solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron-bearing rock, when present, thereby increasing the availability of said mineral-hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; wherein the catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; thereby increasing the rate of hydrogen production and / or lowering the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said aqueous solution. Example 4: The method of any example herein, particularly examples 1-3, wherein the temperature of reaction is 300°C or less. Example 5: The method of any example herein, particularly examples 1-4, wherein the temperature of reaction is lowered to 125°C or less. Example 6: The method of any example herein, particularly examples 1-5, wherein the temperature of reaction is lowered to 100°C or less. Example 7: The method of any example herein, particularly examples 1-6, wherein the temperature of reaction is 90°C or less. Example 8: The method of any example herein, particularly examples 1-7, wherein the temperature of reaction is 75°C or less. Example 9: The method of any example herein, particularly examples 1-8, wherein the hydrogen production rate is increased to greater than 5 × 104kg / sec. Example 10: The method of any example herein, particularly examples 1-9, wherein said contacting occurs in situ with the iron-bearing rock. Example 11: The method of any example herein, particularly examples 1-10, wherein the iron-bearing rock is part of a subsurface formation and / or geological formation. Example 12: The method of any example herein, particularly examples 1-11, wherein the iron-bearing rock comprises (ultra)mafic rock. Example 13: The method of any example herein, particularly examples 1-12, wherein the iron-bearing rock comprises mafic rock. Example 14: The method of any example herein, particularly examples 1-13, wherein the iron-bearing rock comprises (ultra)mafic peridotite, (ultra)mafic pyroxenite, (ultra)mafic hornblendite, (ultra)mafic dunite, or a combination thereof. Example 15: The method of any example herein, particularly examples 1-14, wherein the iron-bearing rock comprises (ultra)mafic peridotite, (ultra)mafic pyroxenite, (ultra)mafic basalt, Archaean banded iron formations, (ultra)mafic dunite, or a combination thereof. Example 16: The method of any example herein, particularly examples 1-15, wherein the iron-bearing rock comprises olivine, pyroxene, amphibole, or a combination thereof. Example 17: The method of any example herein, particularly examples 1-16, wherein the iron-bearing rock comprises olivine, pyroxene, or a combination thereof. Example 18: The method of any example herein, particularly examples 1-17, wherein the iron-bearing rock comprises banded iron formations. Example 19: The method of any example herein, particularly examples 1-18, wherein the iron solubilizer is present (e.g., in the aqueous solution). Example 20: The method of any example herein, particularly examples 1-19, wherein the aqueous solution includes the iron solubilizer. Example 21: The method of any example herein, particularly examples 19-20, wherein the iron solubilizer comprises a halogen containing compound. Example 22: The method of any example herein, particularly examples 19-21, wherein the iron solubilizer comprises an acid. Example 23: The method of any example herein, particularly examples 19-22, wherein the method further comprises injecting CO2to create the iron solubilizer in situ. Example 24: The method of any example herein, particularly examples 19-23, wherein the iron solubilizer comprises an acid and the method further comprises injecting CO2 to create the iron solubilizer in situ. Example 25: The method of any example herein, particularly examples 1-24, wherein the catalyst solubilizer is present (e.g., in the aqueous solution). Example 26: The method of any example herein, particularly examples 1-25, wherein the aqueous solution includes the catalyst solubilizer. Example 27: The method of any example herein, particularly examples 1-26, wherein the iron solubilizer and the catalyst solubilizer are present (e.g., in the aqueous solution). Example 28: The method of any example herein, particularly examples 1-27, wherein the aqueous solution includes the iron solubilizer and the catalyst solubilizer. Example 29: The method of any example herein, particularly examples 1-28, wherein the mineral-hosted catalyst comprises a transition metal, such as W, Mo, Nb, Ta, Re, Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof. Example 30: The method of any example herein, particularly examples 1-29, wherein the mineral-hosted catalyst comprises Ni, Co, Mo, V, or a combination thereof. Example 31: The method of any example herein, particularly examples 1-30, wherein the mineral-hosted catalyst comprises a transition metal, such as Ni, Cu, Pt, Pd, or a combination thereof. Example 32: The method of any example herein, particularly examples 1-31, wherein the mineral-hosted catalyst comprises Ni. Example 33: The method of any example herein, particularly examples 1-32, wherein the mineral-hosted catalyst comprises a platinum group element, such as Pt, Pd, or a combination thereof. Example 34: The method of any example herein, particularly examples 1-33, wherein the catalyst is present (e.g., in the aqueous solution). Example 35: The method of any example herein, particularly examples 1-34, wherein the aqueous solution includes the catalyst. Example 36: The method of any example herein, particularly examples 1-35, wherein the catalyst and the iron solubilizer are present (e.g., in the aqueous solution). Example 37: The method of any example herein, particularly examples 1-36, wherein the aqueous solution includes the catalyst and the iron solubilizer. Example 38: The method of any example herein, particularly examples 1-37, wherein the catalyst and the catalyst solubilizer are present (e.g., in the aqueous solution). Example 39: The method of any example herein, particularly examples 1-38, wherein the aqueous solution includes the catalyst and the catalyst solubilizer. Example 40: The method of any example herein, particularly examples 1-38, wherein the catalyst, the iron solubilizer, and the catalyst are present (e.g., in the aqueous solution). Example 41: The method of any example herein, particularly examples 1-39, wherein the aqueous solution includes the catalyst, the iron solubilizer, and the catalyst solubilizer. Example 42: The method of any example herein, particularly examples 34-41, wherein the catalyst comprises a transition metal, such as W, Mo, Nb, Ta, Re, Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof. Example 43: The method of any example herein, particularly examples 34-42, wherein the catalyst comprises Ni, Co, Mo, V, or a combination thereof. Example 44: The method of any example herein, particularly examples 34-43, wherein the catalyst comprises a transition metal, such as Ni, Cu, Pt, Pd, or a combination thereof. Example 45: The method of any example herein, particularly examples 34-44, wherein the catalyst comprises Ni. Example 46: The method of any example herein, particularly examples 34-45, wherein the catalyst comprises a platinum group element, such as Pt, Pd, or a combination thereof. Example 47: The method of any example herein, particularly examples 34-46, wherein the catalyst comprises a halogen compound, such as a transition metal-halogen compound or a platinum group element-halogen compound, such as a transition metal chloride or a platinum group element chloride. Example 48: The method of any example herein, particularly examples 34-47, wherein the catalyst comprises a nickel-halogen compound, such as a nickel chloride compound. Example 49: The method of any example herein, particularly examples 34-48, wherein the catalyst comprises NiCl2. Example 50: The method of any example herein, particularly examples 2-49, wherein the intermediary catalyst-iron-compound is present (e.g., in the aqueous solution). Example 51: The method of any example herein, particularly examples 2-50, wherein the intermediary catalyst-iron-compound and the iron solubilizer are present (e.g., in the aqueous solution). Example 52: The method of any example herein, particularly examples 2-51, wherein the intermediary catalyst-iron-compound and the catalyst solubilizer are present (e.g., in the aqueous solution). Example 53: The method of any example herein, particularly examples 2-52, wherein the intermediary catalyst-iron-compound and the catalyst are present (e.g., in the aqueous solution). Example 54: The method of any example herein, particularly examples 2-53, wherein the intermediary catalyst-iron-compound, the iron solubilizer, and the catalyst solubilizer are present (e.g., in the aqueous solution). Example 55: The method of any example herein, particularly examples 2-54, wherein the intermediary catalyst-iron-compound, the iron solubilizer, and the catalyst are present (e.g., in the aqueous solution). Example 56: The method of any example herein, particularly examples 2-55, wherein the intermediary catalyst-iron-compound, the catalyst solubilizer, and the catalyst are present (e.g., in the aqueous solution). Example 57: The method of any example herein, particularly examples 2-56, wherein the iron solubilizer, the catalyst solubilizer, the intermediary catalyst-iron-compound, and the catalyst are present (e.g., in the aqueous solution). Example 58: The method of any example herein, particularly examples 1-57, wherein the aqueous solution has an alkaline pH. Example 59: The method of any example herein, particularly examples 1-58, further comprising collecting the produced hydrogen and optionally storing the produced hydrogen. Example 60: The method of any example herein, particularly examples 2-59, further comprising collecting the solubilized iron, solubilized mineral-hosted catalyst, the intermediary catalyst-iron-compound, and / or aqueous catalyst, and optionally recycling them to repeat any of the method of any example herein, particularly examples 2-59. Example 61: The method of any example herein, particularly examples 1-59, further comprising collecting the solubilized iron, solubilized mineral-hosted catalyst, and / or aqueous catalyst, and optionally recycling them to repeat the method of any example herein, particularly examples 1-59. Example 62: The method of any example herein, particularly examples 1-61, wherein the method does not produce a significant amount of greenhouse gases, such as CO2, for example wherein the method produces 1 kilogram or less of CO2equivalent (CO2eq) per kilogram of produced H2. Example 63: The method of any example herein, particularly examples 1-62, wherein the method is economical, for example maintaining costs to $1 per kilogram (kg) of produced hydrogen or less. Example 64: A method of use of hydrogen produced by the method of any example herein, particularly examples 1-63, for energy production and / or industrial purposes. Example 65: A method of use of hydrogen produced by the method of any example herein, particularly examples 1-63, the method comprising using the produced hydrogen for energy production, energy carrier and fuel, energy storage, and / or industrial purposes, including as industrial feedstock, such as, but not limited to, ammonia, methanol, petroleum refining, metallurgy, electronics and glass manufacturing. Example A1: A method of enhanced hydrogen generation from iron-bearing rocks, the method comprising: contacting an iron-bearing rock with an aqueous solution comprising an iron solubilizer, a catalyst solubilizer, and / or a catalyst; wherein the iron solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of iron from the iron-bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen; wherein the catalyst solubilizer, when present in the aqueous solution, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron-bearing rock, when present, thereby increasing the availability of said mineral- hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; wherein the catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; thereby increasing the rate of hydrogen production and / or lowering the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said aqueous solution. Example A2: The method of any examples herein, particularly example A1, wherein the temperature of reaction is lowered to 100°C or less. Example A3: The method of any examples herein, particularly example A1 or example A2, wherein the hydrogen production rate is increased to greater than 5 × 104kg / sec. Example A4: The method of any examples herein, particularly examples A1-A3, wherein said contacting occurs in situ with the iron-bearing rock. Example A5: The method of any examples herein, particularly examples A1-A4, wherein the iron-bearing rock is part of a subsurface formation and / or geological formation. Example A6: The method of any examples herein, particularly examples A1-A5, wherein the iron-bearing rock comprises (ultra)mafic rock. Example A7: The method of any examples herein, particularly examples A1-A6, wherein the iron-bearing rock comprises (ultra)mafic peridotite, (ultra)mafic pyroxenite, (ultra)mafic basalt, Archaean banded iron formations, (ultra)mafic dunite, or a combination thereof. Example A8: The method of any examples herein, particularly examples A1-A7, wherein the iron-bearing rock comprises olivine, pyroxene, or a combination thereof. Example A9: The method of any examples herein, particularly examples A1-A8, wherein the aqueous solution includes the iron solubilizer. Example A10: The method of any examples herein, particularly example A9, wherein the iron solubilizer comprises a halogen containing compound. Example A11: The method of any examples herein, particularly example A9 or example A10, wherein the iron solubilizer comprises an acid. Example A12: The method of any examples herein, particularly examples A1-A11, wherein the aqueous solution includes the catalyst solubilizer. Example A13: The method of any examples herein, particularly examples A1-A12, wherein the aqueous solution includes the iron solubilizer and the catalyst solubilizer. Example A14: The method of any examples herein, particularly examples A1-A13, wherein the mineral-hosted catalyst comprises a transition metal, such as Ni, Cu, Pt, Pd, or a combination thereof. Example A15: The method of any examples herein, particularly examples A1-A14, wherein the mineral-hosted catalyst comprises a platinum group element, such as Pt, Pd, or a combination thereof. Example A16: The method of any examples herein, particularly examples A1-A15, wherein the aqueous solution includes the catalyst. Example A17: The method of any examples herein, particularly examples A1-A16, wherein the aqueous solution includes the catalyst and the iron solubilizer. Example A18: The method of any examples herein, particularly examples A1-A17, wherein the aqueous solution includes the catalyst and the catalyst solubilizer. Example A19: The method of any examples herein, particularly examples A1-A18, wherein the aqueous solution includes the catalyst, the iron solubilizer, and the catalyst solubilizer. Example A20: The method of any examples herein, particularly examples A16-A19, wherein the catalyst comprises a transition metal, such as Ni, Cu, Pt, Pd, or a combination thereof. Example A21: The method of any examples herein, particularly examples A16-A20, wherein the catalyst comprises a platinum group element, such as Pt, Pd, or a combination thereof. Example A22: The method of any examples herein, particularly examples A16-A21, wherein the catalyst comprises a halogen compound, such as a transition metal-halogen compound or a platinum group element-halogen compound, such as a transition metal chloride or a platinum group element chloride. Example A23: The method of any examples herein, particularly examples A1-A22, wherein the aqueous solution has an alkaline pH. Example A24: The method of any examples herein, particularly examples A1-A23, further comprising collecting the produced hydrogen and optionally storing the produced hydrogen. Example A25: The method of any examples herein, particularly examples A1-A24, further comprising collecting the solubilized iron, solubilized mineral-hosted catalyst, and / or aqueous catalyst, and optionally recycling them to repeat the method of any examples herein, particularly examples A1-A24. Example 2A6: The method of any examples herein, particularly examples A1-A25, wherein the method does not produce a significant amount of greenhouse gases, such as CO2, for example wherein the method produces 1 kilogram or less of CO2 equivalent (CO2eq) per kilogram of produced H2. Example A27: The method of any examples herein, particularly examples A1-A26, wherein the method is economical, for example maintaining costs to $1 per kilogram (kg) of produced hydrogen or less. Example A28: A method of use of the produced hydrogen, for energy production and / or industrial purposes. Other advantages which are obvious and which are inherent to the invention will be evident to one skilled in the art. It will be understood that certain features and sub-combinations are of utility and may be employed without reference to other features and sub-combinations. This is contemplated by and is within the scope of the claims. Since many possible embodiments may be made of the invention without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense. The methods of the appended claims are not limited in scope by the specific methods described herein, which are intended as illustrations of a few aspects of the claims and any methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative method steps disclosed herein are specifically described, other combinations of the method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.

Claims

CLAIMS What is claimed is:

1. A method of enhanced hydrogen generation from iron-bearing rocks, the method comprising: contacting an iron-bearing rock with an iron solubilizer, a catalyst solubilizer, an intermediary catalyst-iron-compound, and / or a catalyst; wherein the iron solubilizer, when present, increases the dissolution rate and solubility of iron from the iron-bearing rock, thereby increasing the amount of iron available for reaction with water or hydrogen containing compounds to produce hydrogen; wherein the catalyst solubilizer, when present, increases the dissolution rate and solubility of mineral-hosted catalysts in situ within the iron-bearing rock, when present, thereby increasing the availability of said mineral-hosted catalysts to catalyze the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; wherein the catalyst, when present in the aqueous solution, catalyzes the reaction between iron from the iron-bearing rocks and water or hydrogen bearing compounds to produce hydrogen; thereby increasing the rate of hydrogen production and / or lowering the temperature of reaction necessary to produce said hydrogen relative to the rates and temperature in the absence of said iron solubilizer, catalyst solubilizer, intermediary catalyst-iron-compound, and / or catalyst.

2. The method of claim 1, wherein the iron solubilizer, catalyst solubilizer, intermediary catalyst-iron-compound, and / or catalyst are present in an aqueous solution, such that the method comprises contacting the iron-bearing rock with the aqueous solution comprising the iron solubilizer, the catalyst solubilizer, the intermediary catalyst-iron-compound, and / or the catalyst.

3. The method of any one of claims 1-2, wherein the temperature of reaction is lowered to 125°C or less, preferably 100°C or less.

4. The method of any one of claims 1-3, wherein the hydrogen production rate is increased to greater than 5 × 104kg / sec.

5. The method of any one of claims 1-4, wherein said contacting occurs in situ with the iron-bearing rock.

6. The method of any one of claims 1-5, wherein the iron-bearing rock is part of a subsurface formation and / or geological formation.

7. The method of any one of claims 1-6, wherein the iron-bearing rock comprises (ultra)mafic rock (e.g., mafic and / or ultramafic rock).

8. The method of any one of claims 1-7, wherein the iron solubilizer is present (e.g., in the aqueous solution), and wherein the iron solubilizer comprises a halogen containing compound and / or an acid.

9. The method of claim 8, wherein the method further comprises injecting CO2to create the iron solubilizer in situ.

10. The method of any one of claims 1-9, wherein the catalyst solubilizer is present (e.g., in the aqueous solution).

11. The method of any one of claims 1-10, wherein the mineral-hosted catalyst comprises a transition metal, such as W, Mo, Nb, Ta, Re, Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof.

12. The method of any one of claims 1-11, wherein the catalyst is present (e.g., in the aqueous solution).

13. The method of claim 12, wherein the catalyst comprises a transition metal, such as W, Mo, Nb, Ta, Re, Ni, Cu, Co, Mo, V, Pt, Pd, other platinum group elements (PGE), or a combination thereof.

14. The method of any one of claims 12-13, wherein the catalyst comprises a halogen compound, such as a transition metal-halogen compound or a platinum group element-halogen compound, such as a transition metal chloride or a platinum group element chloride.

15. The method of any one of claims 1-14, wherein the intermediary catalyst-iron-compound is present (e.g., in the aqueous solution).

16. The method of any one of claims 1-15, further comprising collecting the produced hydrogen and optionally storing the produced hydrogen.

17. The method of any one of claims 1-16, further comprising collecting the solubilized iron, solubilized mineral-hosted catalyst, the intermediary catalyst-iron-compound, and / or aqueous catalyst, and optionally recycling them to repeat any of the method of any one of claims 1-16.

18. The method of any one of claims 1-17, wherein the method does not produce a significant amount of greenhouse gases, such as CO2, for example wherein the method produces 1 kilogram or less of CO2 equivalent (CO2eq) per kilogram of produced H2.

19. The method of any one of claims 1-18, wherein the method is economical, for example maintaining costs to $1 per kilogram (kg) of produced hydrogen or less.

20. A method of use of hydrogen produced by the method of any one of claims 1-19, the method comprising using the produced hydrogen for energy production, energy carrier and fuel, energy storage, and / or industrial purposes, including as industrial feedstock, such as, but not limited to, ammonia, methanol, petroleum refining, metallurgy, electronics and glass manufacturing.

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