KR100724555B1 - Metal oxide catalyst for hydrogen generation and method of producing the same - Google Patents

Abstract

The present invention relates to a metal oxide catalyst for producing hydrogen and a method for producing the same, and more particularly, to a catalyst for producing hydrogen containing at least one metal oxide and a method for producing the same. Using the catalyst for producing hydrogen of the present invention has the effect of producing hydrogen with excellent hydrogen production efficiency and low cost.

Metal Oxide, Hydrogen Production, Regeneration, Glycine-Nitrate

Description

Metal oxide catalyst for hydrogen production and its manufacturing method {Metal oxide catalyst for hydrogen generation and method of producing the same}

1 is a graph showing an X-ray diffraction pattern of an iron oxide catalyst according to an embodiment of the present invention.

Figure 2 is a graph showing the hydrogen flow rate over time for the Co ₃ Fe ₂ oxide catalyst prepared according to the glycine-nitrate method.

3 is a graph showing hydrogen flow rate over time for a CoFe ₄ -mixed oxide catalyst prepared by thermal oxidation in a microwave oven.

FIG. 4 is a graph showing hydrogen flow rate over time for a partially calcined iron oxide catalyst prepared through thermal oxidation in a microwave oven.

FIG. 5 is a graph showing hydrogen flow rate over time for an iron oxide catalyst prepared by thermal oxidation in a microwave oven and calcined at 1150 ° C.

6 is a graph showing the maximum hydrogen flow rate according to the Co / Fe molar ratio for the CoFe oxide catalyst prepared according to the glycine-nitrate method.

The present invention relates to metal oxide catalysts or mixed metal oxide catalysts for producing hydrogen from metal borohydrides. The present invention also relates to methods of making metal oxide catalysts, firing methods, activation methods, regeneration methods of deactivated metal oxide catalysts, and the use of oxidation reaction catalysts for various chemical systems.

The transition metal catalysts include oxidation reactions (US Pat. No. 6,124,499), NOx treatment reactions (US Pat. No. 6,916,945), oxidation and ammoxidation reactions of alkanes (US Pat. No. 6,777,571), transesterification reactions. (US Pat. No. 5,350,879), and oxidative coupling reactions of methane (US Pat. No. 4,826,796) as catalysts in various chemical processes. However, metal oxides or mixed metal oxides have not been used or studied in applications for producing hydrogen from metal borohydride solutions. Overall, catalytic activity of metal oxides is closely related to manufacturing conditions, electronic structure, crystallinity, oxidation state, surface area, and the like. In addition, precise control of the surface structure, composition, phase or particle size of the metal oxide can play an important role as various chemical catalysts.

Hydrogen is one of the most important raw materials for the industrial synthesis of chemicals, and recently, it has attracted attention as a clean energy source such as fuel cells. Due to the surge in demand for hydrogen, various methods of storing hydrogen have been developed. As a method of storing hydrogen, there is a method of compressing or liquefying hydrogen or adsorbing hydrogen to carbon nanotubes, activated carbon, metals or metal alloys. However, the method of compressing or liquefying hydrogen can relatively easily control the flow rate and pressure of hydrogen, but the safety is a problem, and the method of adsorbing and storing hydrogen has a problem of low energy density per unit volume and a slow reaction. Recently, a method of producing hydrogen from an aqueous solution of borohydride using a catalyst has attracted much attention from researchers because it can stably and safely supply hydrogen.

It is well known that hydrogen gas can be produced by hydrolyzing sodium borohydride using an acid, a transition metal, or a salt thereof as a catalyst (Kaufam, CM and Sen, B., J. Chem. Soc. Dalton Trans). . 1985, 307-313). US Patent No. 6,534,033 discloses a process for producing hydrogen from a stabilized metal borohydride solution using a transition metal catalyst. These metal catalysts include ruthenium, rhodium, or cobalt metals supported on various substrates and exhibit high activity in hydrogen production. Other metal catalysts include silver, iron, nickel, copper, etc. Experiments have shown no or low activity at room temperature. Metal catalysts such as copper and nickel show improved activity after heating in a nitrogen atmosphere at temperatures of 600 ° C. to 800 ° C. The use of high performance metal catalysts such as ruthenium, rhodium or platinum is too expensive and not economical for single use in various applications.

Recently published Kojima, Y. et al., Int. According to J. Hydrogen Energy , 2002 , 27, 1029-1034, Toyota Central R & D Laboratories, Inc. reported that catalysts containing platinum and LiCoO ₂ showed high catalytic activity in hydrogen production. This high catalytic activity is due to the synergistic effect of finely divided platinum on the metal oxide backbone. However, this system still uses precious metals such as platinum, which is not attractive for practical use because of high manufacturing costs. In view of practicality, there is a need for a catalyst that is excellent in hydrogen production efficiency and low in production cost.

The first technical problem to be achieved by the present invention is to provide a catalyst for producing hydrogen with excellent hydrogen production efficiency and low production cost.

The second technical problem to be achieved by the present invention is to provide a method for producing a catalyst for producing hydrogen with excellent hydrogen production efficiency and low production cost.

The third technical problem to be achieved by the present invention is to provide a method for producing the catalyst for producing hydrogen.

The fourth technical problem to be achieved by the present invention is to provide a method for regenerating the catalyst for producing hydrogen.

The present invention provides a catalyst for producing hydrogen containing at least one metal oxide in order to achieve the first technical problem.

The present invention provides a method for producing a catalyst for producing hydrogen for producing a metal oxide catalyst from a metal source comprising the step of heating the metal to a temperature of 200 ℃ to 1200 ℃ in air or ozone atmosphere to achieve the second technical problem. .

In another aspect, the present invention provides a method for producing a catalyst for producing hydrogen for producing a metal oxide catalyst from a metal compound, comprising the step of decomposing the metal compound by heating as another method for achieving the second technical problem.

The present invention provides a method for producing hydrogen comprising contacting the metal oxide catalyst with a solution comprising a metal borohydride, a base and a proton donor solvent to achieve the third technical problem.

The present invention comprises the steps of sonicating the deactivated metal oxide catalyst in a solvent to achieve the fourth technical problem; Washing the catalyst with a solvent; And heating the catalyst to 200 ° C. to 1200 ° C., to provide a method for regenerating a metal oxide catalyst for producing inactivated hydrogen.

Hereinafter, the present invention will be described in more detail.

The present invention provides an inexpensive metal oxide catalyst for producing hydrogen having high catalytic activity. The present invention also provides a method for producing a supported or unsupported catalyst based on metal oxides and a method for producing hydrogen using the catalyst.

Hereinafter, with reference to the accompanying drawings showing a preferred embodiment of the present invention will be described in more detail the present invention. However, the present invention may be embodied in other forms and should not be construed as limited to the embodiments set forth herein.

The present invention provides a catalyst for producing hydrogen comprising at least one metal oxide. The metal oxide may comprise one or more transition metal oxides.

The metal oxide catalyst for producing hydrogen of the present invention is Sc, T, V, Cr, Mn, Fe, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf , Ta, W, Re, Os, Ir, Pt, Au, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and mixtures thereof One or more transition metal oxides, or mixtures thereof, including oxides of metal elements to be formed. The transition metal oxide may have a monovalent (+1) or multivalent (+2, +3, +4, ...) oxidation state. The transition metal oxide more preferably comprises an oxide of a metal element selected from the group consisting of Fe, Co, Ni, Cu, Ru, Rh and mixtures thereof. In another embodiment, the metal oxide catalyst may include one or more transition metal oxides combined with one or more non-transition metal oxides. The non-transition metal may be Li, Na, Sr, K, Rb, Cs, Fr, Mg, Ca, Sr, Ba, Ra, Al, Si, Fe, Ga, In, Sn, Pb, or a mixture thereof. have. Some mixed metal oxides have the effect of inhibiting hydrogen production. Oxides of metal elements selected from Mo, Zn, V, W, and the like having an effect of inhibiting hydrogen generation are useful for controlling the flow rate of hydrogen. By combining these metal elements with active metal oxides including Fe, Co, Cu, Ni, Ru, Rh and mixtures thereof, the desired hydrogen flow rates and controlled activation times can be achieved for certain applications.

For high catalytic activity and economy, the present invention provides, but is not limited to, mixed metal oxide catalysts for the production of hydrogen comprising oxides of metal elements selected from Fe, Co, Cu, Ni, Ru, Rh and combinations thereof. . The oxidation state of these metals may be monovalent, two or more polyvalents, or a mixture of monovalent and two or more polyvalents. In particular, the metal oxide may be a Co-Fe oxide (cobalt oxide-iron oxide). At this time, the molar ratio of cobalt to iron may be 0.001 to 1000. If the molar ratio of cobalt to iron is less than 0.001, little hydrogen is produced, and if the molar ratio of cobalt to iron is greater than 1000, it is uneconomical because the hydrogen flow rate is no longer increased and cobalt is more expensive than iron.

These mixed metal oxide catalysts not only show high catalytic activity due to synergistic effects, but also show much shorter activation times than single metal oxide catalysts. Metal oxides or mixed metal oxides may be combined with ferromagnetic materials to facilitate separation of the catalyst used.

The metal oxide catalyst is in the form of a powder, chip, disk, rod, wire, mesh, bead, porous or nonporous monolith, porous strip, or nonporous strip, or a metal, ceramic, polymer, glass, Fibers, fabrics, textiles, wovens, nonwovens, alloys, zeolites, molecular sieves, ion exchange resins, graphite, metal oxides, metal carbides, metal bores Metal oxide particles supported on a substrate comprising a cargo, metal nitride, and mixtures thereof.

That is, the metal oxide may be supported on the support, or may be in the form of an unsupported catalyst not supported on the support.

The surface area of the cobalt oxide catalyst may be 1 m ² / g to 500 m ² / g.

The preparation of the metal oxides of the present invention may be by thermal oxidation or hydrothermal oxidation of metals or by decomposition processes of various metal compounds. Unsupported metal oxide catalysts can be prepared by thermal oxidation of metals in an oxidizing atmosphere such as air or ozone. It is preferable that the temperature of the said thermal oxidation is 200 degreeC-1200 degreeC normally, and 400 degreeC-800 degreeC. If the temperature of thermal oxidation is less than 200 ° C., oxidation does not occur sufficiently so that metal oxides are not produced well. If the temperature of thermal oxidation exceeds 1200 ° C., the temperature is melted to increase density and decrease activity.

The degree to which the surface of the metal oxide is oxidized may be known from the color of the oxidized metal. The simplest method for producing a metal oxide is to thermally oxidize it by heating using a heating space in an air atmosphere, for example, microwaves. The microwave heating process not only oxidizes the metal powder but also sinters the metal oxide particles. The time required for firing the cobalt metal particles is about 0.5 to 20 minutes depending on the power of the microwave and the power of the microwave is preferably 500 W to 950 W. Alternatively, the metal may be oxidized and fired by an open frame or electric discharge heating in an air or ozone atmosphere. Structural analysis on these metal oxide samples can be performed using the X-ray diffraction (XRD) method. 1 is an XRD pattern showing the complete conversion of metal iron to iron oxide.

The heating space may be, for example, but not limited to, a microwave oven, an electric high temperature furnace, an electric heating oven, a heat gun, a hot plate, or a combination thereof. In the heating space, firing may occur at the same time as the metal is oxidized.

An alternative method of producing metal oxides is to oxidize the metal at 200 ° C. to 1200 ° C., preferably 400 ° C. to 800 ° C. for 10 minutes to 12 hours, preferably 1 hour to 2 hours, in an electric furnace in an air or ozone atmosphere. will be. Metal oxides can also be prepared by hydrothermal oxidation or steam oxidation. These processes can take more time than microwave heating processes and often require additional heat treatment to use the catalyst for hydrogen production.

Another embodiment of the present invention is to prepare a metal oxide catalyst by pyrolyzing a metal compound. The precursor of the metal oxide catalyst can be a metal fluoride, metal chloride, metal bromide, metal iodide, metal nitrate, metal carbonate, metal hydroxide, metal borate, metal acetate, metal oxalate, or organometallic compound. The glycine-nitrate method can be used to produce metal oxides or mixed metal oxide powders having a high surface area. At this time, the size and porosity of the metal oxide particles can be controlled by adjusting the amount of glycine. Glycine-nitrate methods are well known in the art, see for example http://picturethis.pnl.gov/PictureT.nsf/All/3QWS7T?opendocument.

Supported metal oxide catalysts include metals, ceramics, polymers, glass, fibers, fabrics, textiles, wovens, nonwovens, alloys, zeolites, and molecular sieves. Through the decomposition process of metal oxides bound to, encapsulated in, or applied onto substrates comprising, ion exchange resins, graphite, metal oxides, metal carbides, metal borides, metal nitrides, and mixtures thereof. Are manufactured. Another method of preparing the supported metal oxide catalyst is to heat and oxidize the coated metal on the substrate in an air or ozone atmosphere. Coating of the metal film on the substrate may be, for example, by electroplating or electroless plating, but is not limited thereto.

The hydrogen production process according to the invention can be initiated by contacting a metal oxide catalyst with a solution comprising a metal borohydride, a base and a proton donor solvent. The metal borohydride may be selected from the group consisting of lithium borohydride, sodium borohydride, potassium borohydride, ammonium borohydride, tetramethyl ammonium borohydride, and mixtures thereof. The base used here serves to stabilize the metal borohydride in solution. Conventional bases used in metal borohydride solutions are, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium sulfide, sodium zincate, sodium gallate Sodium gallate, sodium silicate, and mixtures thereof, but is not limited thereto.

The generation of hydrogen from the metal borohydride solution is caused by solvolysis of the metal borohydride by the proton donor solvent. Therefore, any proton donor solvent can be used for solvolysis of the metal borohydride of the present invention. Preferred examples of such solvents include water; All alcohols including ethylene glycol, glycerol, methanol, ethanol, isopropanol, isobutanol, propanol, propanediol, butanol, and mixtures thereof, but are not limited thereto. Another method for producing hydrogen can be initiated by mixing a proton donor solvent with a solid system comprising a metal oxide catalyst and a solid metal borohydride. The hydrogen production of this process can be controlled by controlling the amount of solvent added to the solid mixture of the metal oxide catalyst and the solid metal borohydride.

When using the newly prepared metal oxide catalyst, it may take several minutes to generate hydrogen gas from the metal borohydride solution. Surface activation occurs by immersing the catalyst in the metal borohydride solution for 1-30 minutes. Once the catalyst is activated, the amount of hydrogen produced is observed to increase immediately. In order to accelerate the surface activation of the newly prepared metal oxide, heating may be required. Preferred heating temperatures may be from 30 ° C. to 100 ° C., preferably from 40 ° C. to 80 ° C. However, if the hydrogen production process does not require an immediate reaction, this activation process may be unnecessary. In general, activation of the metal oxide catalyst can be related to the amount of catalyst, the concentration of metal borohydride and stabilizer, and the particle size of the catalyst. Mixed metal oxide catalysts often show shorter activation times in hydrogen production.

After multiple uses of the metal oxide catalyst or mixed metal oxide catalyst, catalyst activity decreases due to surface contamination and / or partial reduction. The deactivated metal oxide catalyst may comprise (1) sonicating the catalyst in a solvent such as deionized water; (2) washing the catalyst several times with a solvent such as deionized water; (3) The catalyst may be reactivated through a process such as heating the catalyst to 200 ° C to 1200 ° C, preferably 400 ° C to 800 ° C. The solvent is preferably deionized water, but is not limited thereto. The heating may be performed in a heating space such as, but not limited to, a high temperature furnace, an electric heating oven, a heat gun, a hot plate, a microwave oven, an electric heating furnace, or a combination thereof.

If the heating temperature is less than 200 ℃ deactivated cobalt oxide catalyst is not properly reactivated, if the heating temperature exceeds 1200 ℃ has a disadvantage in that the density is increased and the activity is reduced by melting.

Hereinafter, the configuration and effects of the present invention will be described in more detail with specific examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention.

Example 1 Molded Preparation of a CoFe ₄ -Oxide Catalyst by Thermal Oxidation Using Microwave

1.7678 g of Co metal powder and 4.468 g of Fe metal powder were mixed for 10 minutes by a mechanical agitator. Co-4Fe metal powder was mixed with deionized water to prepare a paste of Co-4Fe metal. The paste was flattened on a ceramic plate about 2-3 mm thick and cut into pieces having a size of 2-3 mm. The paste thus shaped was dried by heating in a microwave oven with a power of 950 W for 10 minutes.

<Example 2> Preparation of unsupported iron oxide catalyst through thermal oxidation process using microwave

20 g of metal iron powder was thermally oxidized in a microwave oven for 10 minutes to prepare an iron oxide catalyst. The output of the microwave was set to 950 W. Within a minute of generating the microwaves, the iron metal powder began to glow red. Microwave heating of the sample was continued for 10 minutes. After the heating was completed, a black sample was produced.

Example 3 Preparation of Mixed Metal Oxide Catalyst Through Thermal Oxidation Process Using Microwave

Mixed metal powders were thermally oxidized in a microwave oven for 10 minutes to prepare various mixed-metal oxide catalysts. Other preparation conditions were the same as in Example 1. The two metal powders were mixed in a mechanical mixer at a molar ratio of 50:50 before heating to produce a mixed-metal oxide catalyst. Table 2 shows the combinations of metal oxides mixed in a molar ratio of 50:50.

Table 2: Metal Oxide Theorem Bonded at a Molar Ratio of 50:50

Vanadium (V) Copper (Cu) Zinc (Zn) Molybdenum (Mo) Fe FeV-oxide FeCu-oxide FeZn-oxide FeMo-oxide Cobalt (Co) CoV-oxide CoCu-oxide CoZn-oxide CoMo-Oxide

Example 4 Preparation of Formation of Iron Oxide Catalyst by Thermal Oxidation Process Using Microwave

30 g of ferrous metal powder was flattened onto a ceramic plate and sealed with a flat plastic plate. The plate of sealed ferrous metal powder was divided into pieces of 2-3 mm size and heated in a microwave oven at 950 W for 10 minutes. Thereafter, heating in an electric furnace at 1150 ° C. for 2 hours was performed for further calcination of the iron oxide catalyst. The fired sample was ground for X-ray diffraction analysis (XRD). 1 shows an XRD pattern of iron oxide samples synthesized in a microwave oven. Looking at the XRD phase, there is no portion representing the Fe metal phase, which means that it is completely oxidized.

Example 5 Preparation of Unsupported Iron Oxide Catalyst in High Temperature Heating Furnace

An alumina crucible containing ferrous metal powder was placed in a high temperature furnace in an air atmosphere and heated to 800 ° C. for 2 hours. As a result, the sample was oxidized and fired at the same time.

Example 6 Preparation of Unsupported Cobalt Oxide-Iron Oxide Catalyst Using Glycine-Nitrate Combustion Process

A cobalt oxide-iron oxide catalyst was synthesized by varying the molar ratio of cobalt and iron using a glycine-nitrate process. In this process, an aqueous solution comprising glycine and a mixture of cobalt nitrate / iron chloride or cobalt chloride / iron nitrate was prepared and heated so that excess water was evaporated to run out. Continued heating of the residual material caused self-ignition, resulting in black fine powder. In the present invention, the molar ratio of glycine and metal salt was 1: 1. 6 shows the maximum hydrogen flow rate of the Co—Fe oxide catalyst having a molar ratio of Co: Fe of 0.25 to 9.

Example 7 Preparation of Supported Iron Oxide-Cobalt Oxide Catalysts

Equal moles of cobalt and iron nitrate were dissolved in deionized water to prepare a solution of cobalt and iron nitrate at 2 M concentration. 2 ml of the resulting solution was placed in a 100 ml beaker containing 3 g of molecular sieve (Yakuri Pure Chemicals Co. LTD, Osaka, Japan). The molecular sieves impregnated with cobalt and iron ions were dried in an oven at 100 ° C. for 1 hour and then heated to a maximum temperature on a hotplate for 1 hour.

Example 8 Hydrogen Production Experiment

Hydrogen generation experiments were performed to measure the flow rate of the hydrogen produced. Several metal oxide and mixed-metal oxide samples were used. Hydrogen production experiments consisted of sodium borohydride containing 80.5% by weight of deionized water, 3.5% by weight of NaOH, and 16% by weight of NaBH _{4 in} a reaction vessel containing a predetermined amount (0.01 to 0.3 g) of a metal oxide or mixed-metal oxide powder sample. The experiment was performed by adding 20 ml of solution.

The flow rate of the generated hydrogen was measured using a mass flow controller (MFC) connected to a computer. 2-6 show graphs of hydrogen flow rates for various metal oxide catalysts.

2-5 are relationships of hydrogen flow rate and time for various metal oxide catalysts. In the case of the Co ₃ Fe ₂ -oxide catalyst prepared using the glycine-nitrate process of the present invention, the flow rate of hydrogen peaked at about 50,000 ml / min · g without temperature control (see FIG. 2). . On the other hand, the CoFe ₄ -oxide catalyst prepared by the thermal oxidation process using a microwave showed a maximum hydrogen flow rate of 3065 ml / min. G, but activation occurred quickly (see Figure 3). The maximum hydrogen flow rates of the iron oxide samples were 2193 ml / min g and 2473 ml / min respectively for partially calcined iron oxide (microwave heating) and calcined iron oxide (microwave heating and further heating at 1150 ° C.). g (see FIGS. 4 and 5). Although additional heat treatment did not make a big difference in hydrogen flow rate, calcined catalysts were more desirable in terms of ease of use and mechanical strength. In Co-Fe oxide systems prepared from the glycine-nitrate process, decreasing the iron content increased the maximum hydrogen flow rate but was constant when the Co / Fe molar ratio was 1.5 or higher (see FIG. 6). The hydrogen flow rate may depend on the concentration of sodium borohydride, the particle size and amount of the catalyst, the composition of the heterometal, and the like. The maximum hydrogen flow rates of the various mixed metal oxides are summarized in Table 1. Unlike Co-Fe oxide systems, iron oxide or cobalt oxide combined with zinc oxide had no catalytic activity in hydrogen production. Other metal oxides combined with cobalt oxide showed relatively weak activity in hydrogen production.

TABLE 1 Maximum hydrogen flow rate of bound metal oxide catalysts (ml / min.g)

V-oxide Cu-oxide Zn-oxide Mo-oxide Fe-oxide 0 453 0 0 Co-oxide 227 13260 0 2153

Although described in detail with respect to preferred embodiments of the present invention as described above, those of ordinary skill in the art, without departing from the spirit and scope of the invention as defined in the appended claims Various modifications may be made to the invention. Therefore, changes in the future embodiments of the present invention will not be able to escape the technology of the present invention.

Use of the metal oxide catalyst for producing hydrogen of the present invention has the effect of producing hydrogen with excellent hydrogen production efficiency and low cost.

Claims (26)

A catalyst for producing hydrogen for the production of hydrogen from metal borohydrides consisting of one or more metal oxides, except oxides of Fe and V, oxides of Fe and Zn, oxides of Fe and Mo, and oxides of Co and Zn. The catalyst for producing hydrogen of claim 1, wherein the metal oxide comprises one or more transition metal oxides. delete The method of claim 2, wherein the transition metal is Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Catalyst for producing hydrogen, comprising Ta, W, Re, Os, Ir, Pt, Au, or a mixture thereof. 2. The catalyst for producing hydrogen according to claim 1, wherein the metal oxide comprises at least an oxide of Fe, Co, Cu, Ni, Ru, Rh or a mixture thereof. delete 2. The catalyst for producing hydrogen according to claim 1, wherein the metal oxide is a metal oxide having an oxidation state of 1 or 2 or more, or a mixture thereof. The catalyst for producing hydrogen according to claim 1, wherein the metal oxide is Co—Fe oxide, and the molar ratio of Co to Fe is 0.001 to 1000. The catalyst for producing hydrogen of claim 1, wherein the metal oxide is in an unsupported form. 10. The catalyst for producing hydrogen according to claim 9, wherein the catalyst is in the form of powder, chip, disc, rod, wire, mesh, bead, monolith, porous strip, or nonporous strip. The catalyst for producing hydrogen according to claim 1, wherein the metal oxide is supported on the carrier. The method of claim 11, wherein the support is selected from metals, ceramics, polymers, glass, fibers, fabrics, textiles, wovens, nonwovens, alloys, zeolites, molecular sieves. molecular sieves), ion exchange resins, graphite, metal oxides, metal carbides, metal borides, metal nitrides, and mixtures thereof. A metal source comprising heating the metal to a temperature of 200 ° C. to 1200 ° C. in an air or ozone atmosphere, provided that sources of Fe and V, sources of Fe and Zn, sources of Fe and Mo, sources of Co and Zn A method for producing a catalyst for producing hydrogen for producing hydrogen from a metal borohydride. The method for producing a catalyst for producing hydrogen according to claim 13, wherein the oxidation due to the heating is thermal oxidation, hydrothermal oxidation or steam oxidation. The method of claim 13, wherein the oxidation and firing of the metal oxide prepared from the metal source is performed by a microwave oven, an electric high temperature furnace, an electric heating oven, a heat gun, a hot plate, or a combination thereof. The method for producing a catalyst for producing hydrogen. A glycine nitrate process comprising the step of decomposing the metal compound (except for the metal compound of Fe and V, the metal compound of Fe and Zn, the metal compound of Fe and Mo, and the metal compound of Co and Zn) by heating, A method for producing a catalyst for producing hydrogen for producing hydrogen from a metal borohydride for producing a metal oxide catalyst from a metal compound comprising a. 17. The metal compound of claim 16, wherein the metal compound is a metal fluoride, metal chloride, metal bromide, metal iodide, metal nitrate, metal carbonate, metal hydroxide, metal borate, metal acetate, metal oxalate, or organometallic compound Method for producing a catalyst for producing hydrogen, characterized in that. delete A method of producing hydrogen comprising contacting a metal oxide catalyst of claim 1 with a solution comprising a metal borohydride, a base and a proton donor solvent. 20. The method of claim 19, wherein said metal borohydride is selected from the group consisting of lithium borohydride, sodium borohydride, potassium borohydride, and mixtures thereof. The method of claim 19, wherein the base is lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium sulfide, sodium zincate, sodium gallate, sodium silicate And a mixture thereof. 20. The hydrogen production according to claim 19, wherein the proton donor solvent is selected from the group consisting of water, ethylene glycol, glycerol, methanol, ethanol, isopropanol, isobutanol, propanol, propanediol, butanol, and mixtures thereof. Way. A method of producing hydrogen comprising contacting a proton donor solvent with a solid mixture comprising a metal borohydride and the metal oxide catalyst of claim 1. (a) sonicating a deactivated metal oxide catalyst (except for oxides of Fe and V, oxides of Fe and Zn, oxides of Fe and Mo, oxides of Co and Zn) in a solvent; (b) washing the catalyst with a solvent; And (c) heating the catalyst to 200 ° C to 1200 ° C. 25. The metal for producing deactivated hydrogen according to claim 24, wherein the heating is performed by a microwave oven, a high temperature furnace, an electric heating oven, a heat gun, a hot plate or a combination thereof. Regeneration method of oxide catalyst. 25. The method of claim 24, wherein the solvent is deionized water.

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