TWI498161B - Catalyst for hydrogen generation and manufacturing method therefor - Google Patents

Description

Catalyst for catalytic hydrogen evolution reaction and manufacturing method thereof

The present invention relates to a catalyst and a method of manufacturing the same, and more particularly to a catalyst for catalytic hydrogen evolution reaction and a method of producing the same.

Nowadays, with the gradual depletion of limited energy sources, fuel cells have become the mainstream of many green energy sources. For a hydrogen fuel cell, the fuel is hydrogen, oxidant oxygen. Since hydrogen is a dangerous flammable gas and the storage conditions are severe, it is usually used as an aqueous hydrogen source or a hydrogen storage material containing hydrogen as a hydrogen source, and hydrogen is extracted therefrom for use in a fuel cell.

However, today's fuel cells are still not widely used in daily life. One is that the rate of hydrogen evolution reaction during the process of extracting hydrogen from a hydrogen source is too slow, resulting in insufficient application. In this case, if a sufficient amount of hydrogen is to be obtained, the device will be bulky. The second is that even if a hydrogen-releasing catalyst is used to increase the hydrogen evolution rate of the hydrogen source, a nano-scale hydrogen-releasing catalyst must be used to achieve a high hydrogen-releasing rate with its high surface area. However, the conventional nano-scale hydrogen-releasing catalyst is difficult to mass-produce rapidly, and the cost of raw materials and equipment is high, which makes it difficult to commercialize. Among them, conventional hydrogen-releasing catalysts include, for example, noble metal ruthenium (Ru), rhodium (Rh), and non-precious metal cobalt (Co), nickel (Ni), iron (Fe), manganese (Mn), and copper (Cu). The high-cost precious metals, antimony and antimony can provide far more hydrogen release efficiency than non-precious metals.

Please refer to FIG. 1 , which shows a schematic diagram of a conventional hydrogen release reaction catalyst. The conventional hydrogen release reaction catalyst 100 includes a catalyst carrier 110 and a metal catalyst layer 120. The conventional catalyst carrier 110 is, for example, alumina, and the metal catalyst layer 120 is, for example, ruthenium (Ru), cobalt (Co), nickel (Ni), iron (Fe), manganese (Mn) or copper (Cu). Moreover, the conventional hydrogen release reaction catalyst 100 is usually produced by coating a mixture containing a metal catalyst on the surface of the catalyst carrier 110, and then applying a high temperature of about 550 ° C to form a metal catalyst layer 120. The surface of the media carrier 110. After the high temperature process at 550 ° C, the surface of the catalyst carrier 110 also produces metal oxides, which must be reduced to metals, and the reduction process requires the use of hydrogen at higher temperatures (eg, about 700 ° C). To reduce the metal. Therefore, the conventional manufacturing method requires a vacuum system or a protective atmosphere in addition to the use of a high temperature system, and the manufacturing cost is relatively high. Furthermore, the use of hydrogen to reduce metals at high temperatures is also extremely dangerous.

The present invention relates to a catalyst for catalytic hydrogen evolution reaction and a method for producing the same, which utilizes a chelation reaction and a reduction reaction to have a plurality of metal catalyst ions on the surface of a catalyst carrier, or a plurality of metal catalyst atoms, or It is a metal catalyst nanostructure, or a combination of a metal catalyst atom and a nanostructure. In addition to further increasing the rate of hydrogen evolution reaction, it is more capable of rapid mass production and low manufacturing cost to achieve the goal of commercialization.

According to a first aspect of the invention, a method of producing a catalyst for catalyzing a hydrogen evolution reaction is provided. This manufacturing method includes the following steps. First, an aqueous solution is provided which contains a plurality of metal catalyst ions. Next, a plurality of catalyst carriers are provided, each of which has a plurality of chelating units. Then, the catalyst carriers are placed in an aqueous solution to sequester the metal catalyst ions in the aqueous solution to the chelating units on the surface of each catalyst carrier to form a plurality of catalysts. Then, collect these catalysts.

According to a second aspect of the invention, a catalyst for catalyzing a hydrogen evolution reaction is proposed. The catalyst comprises a catalyst carrier of an ion exchange resin and a plurality of metal catalyst atoms. These metal catalyst atomic systems are formed on the surface of the catalyst carrier. In addition, all or a part of the metal catalyst atoms may be subjected to a reduction reaction to form a plurality of metal catalyst nanostructures on the surface of the catalyst carrier.

According to a third aspect of the invention, a catalyst for catalyzing a hydrogen evolution reaction is proposed. The catalyst comprises a catalyst carrier of an ion exchange resin and a plurality of metal catalyst ions. The surface of the catalyst carrier has a plurality of chelating groups. These metal catalyst ions are each sequestered to a chelating group on the surface of the catalyst carrier.

In order to make the above-mentioned contents of the present invention more comprehensible, the following specific embodiments, together with the drawings, are described in detail below:

The invention provides a manufacturing method capable of rapidly preparing a catalyst for catalytic hydrogen release reaction, which not only has a simple preparation process, but can be mass-produced quickly and at low cost, and the prepared catalyst has a high hydrogen production rate. The first and second embodiments of the present invention are set forth below. However, the catalyst structure and reaction steps set forth in the examples are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, the illustrations in the embodiments also omit unnecessary elements in order to clearly show the technical features of the present invention.

First embodiment

Referring to FIG. 2, there is shown a schematic diagram of a catalyst for catalyzing a hydrogen evolution reaction in accordance with a first embodiment of the present invention. In the first embodiment, the catalyst 200 for catalyzing the hydrogen evolution reaction comprises a catalyst carrier 210 of an ion exchange resin and a plurality of metal catalyst ions 220. The surface of the catalyst carrier 210 has a plurality of chelating groups 211. The metal catalyst ions 220 are chelated to the chelating groups 211 on the surface of the catalyst carrier 210, respectively.

The catalyst carrier 210 has a particle diameter of 1 μm to 10 mm. The catalyst carrier 210 may optionally be a cationic ion exchange resin such as MSC-1B (The Dow Chemical Company), DowEX-HCR-W2 (The Dow Chemical Company), MSC-1A (The Dow Chemical Company), Amberlyst. -15 (The Dow Chemical Company), Dow EX-22 (The Dow Chemical Company), Dow EX-88 (The Dow Chemical Company), IR-120 (The Dow Chemical Company). Alternatively, the catalyst carrier 210 may also be an anionic ion exchange resin such as A-26 (The Dow Chemical Company), IRA-400 (The Dow Chemical Company), IRA-900 (The Dow Chemical Company), DowEX. -550A (The Dow Chemical Company), DowEX-MSA-1 (The Dow Chemical Company), DowEX-MSA-2 (The Dow Chemical Company), A-36 (The Dow Chemical Company). In addition, the metal catalyst ions 220 are selected from the group consisting of ruthenium (Ru), cobalt (Co), nickel (Ni), iron (Fe), manganese (Mn), and copper (Cu). At least one metal catalyst ion.

The catalyst 200 for catalyzing a hydrogen evolution reaction of the present embodiment can be used to catalyze a hydrolysis reaction of a hydride with water to generate hydrogen. The hydride is selected from lithium aluminum hydride (LiAlH ₄ ), sodium aluminum hydride (NaAlH ₄ ), aluminum magnesium hydride (Mg(AlH ₄ ) ₂ ), calcium aluminum hydride (Ca(AlH ₄ ) ₂ ), hydroboration Lithium (LiBH ₄ ), sodium borohydride (NaBH ₄ ), potassium borohydride (KBH ₄ ), bismuth borohydride (Be(BH ₄ ) ₂ ), magnesium borohydride (Mg(BH ₄ ) ₂ ), calcium borohydride ( A group consisting of Ca(BH ₄ ) ₂ ), lithium hydride (LiH), sodium hydride (NaH), magnesium hydride (MgH ₂ ), and calcium hydride (CaH ₂ ). Here, before the powder of the catalyst 200 is used for the hydride hydrolysis reaction, the powder of the catalyst 200 may be pulverized into particles having a size of about 1 μm to 10 mm to increase the total surface area. When it is used to catalyze the hydrolysis reaction of a hydride with water, the hydrogen generation can be further accelerated.

Hereinafter, a method of manufacturing the catalyst 200 of the present embodiment will be described with reference to a flowchart. Referring to FIG. 3 and FIG. 4, FIG. 3 is a flow chart showing a method for manufacturing a catalyst according to a first embodiment of the present invention, and FIG. 4 is a schematic view showing a catalyst for manufacturing according to a first embodiment of the present invention. In the first embodiment, the catalyst 200 manufacturing method includes the following steps.

First, as shown in step S31, an aqueous solution containing the metal catalyst ions 220 is provided. Wherein, the aqueous solution is a metal salt aqueous solution, and the molar concentration of the metal catalyst ion 220 in the aqueous solution is about 0.001 M to 10 M depending on the application.

Next, as shown in step S32, a plurality of catalyst carriers 210 are provided. Each of the catalyst carriers 210 has a plurality of chelating units 211. Further, in step S32, the catalyst carriers 210 may be pulverized into particles having a uniform size and a particle size range of between 1 μm and 10 mm by means of polishing or the like.

Then, as shown in step S33, the catalyst carriers 210 are placed in an aqueous solution to form a plurality of catalysts 200. In this step S33, the metal catalyst ions 220 in the aqueous solution are sequestered to the chelating unit 210 on the surface of each of the catalyst carriers 210 to form the catalysts 200.

Then, as shown in step S34, the catalysts 200 are collected. In this step S34, the steps of taking out the catalysts 200, cleaning the catalysts 200, and drying the catalysts 200 are included. Here, in the step of drying the catalyst 200, the catalyst 200 is dried in a vacuum atmosphere or in an inert gas.

Further, in the present embodiment, the operating temperature of the catalyst 200 is set to be between -20 ° C and 80 ° C. Therefore, in the present embodiment, the operating temperature at which the catalyst 200 is manufactured can be regarded as a room temperature operation without using a high temperature system. In addition, in this embodiment, the chelation reaction is used to use the ion exchange resin as a catalyst carrier, and the metal catalyst ions can be directly captured on the surface thereof, and the chelation of the metal catalyst ions can be controlled by controlling the concentration and time. Quantity. Therefore, the catalyst manufacturing process according to the first embodiment of the present invention is simple, in addition to being fast and mass-produced, and having the advantage of low equipment cost.

Second embodiment

Please refer to FIG. 5, which is used to illustrate according to the second embodiment of the present invention. Schematic diagram of a catalyst for catalytic hydrogen evolution reaction. In the second embodiment, the catalyst 300 for catalyzing the hydrogen evolution reaction comprises a catalyst carrier 310 of an ion exchange resin and a plurality of metal catalyst atoms. These metal catalyst atomic systems are formed on the surface of the catalyst carrier 310. Moreover, the metal catalyst atoms form a plurality of metal catalyst nanostructures 320 on the surface of the catalyst carrier 310, or a plurality of metal catalysts are formed on the surface of the catalyst carrier only by a portion of the metal catalyst atoms. Nanostructure 320. In embodiments, the size of the metal catalyst nanostructures is less than 100 nm.

The catalyst carrier 310 has a particle diameter of 1 μm to 10 mm. Similarly, the catalyst carrier 310 may optionally be a cationic ion exchange resin such as MSC-1B, DowEX-HCR-W2, MSC-1A, Amberlyst-15, DowEX-22, DowEX-88, IR-120. Alternatively, the catalyst carrier 310 may also be an anionic ion exchange resin such as A-26, IRA-400, IRA-900, DowEX-550A, DowEX-MSA-1, DowEX-MSA-2, A-36. . In addition, the metal catalyst atoms are selected from at least one of the group consisting of ruthenium (Ru), cobalt (Co), nickel (Ni), iron (Fe), manganese (Mn), and copper (Cu). A metal catalyst.

Similarly, the catalyst 300 for catalytic hydrogen evolution reaction of the present embodiment can be used to catalyze the hydrolysis reaction of a hydride with water to generate hydrogen. The hydride is selected from lithium aluminum hydride (LiAlH ₄ ), sodium aluminum hydride (NaAlH ₄ ), aluminum magnesium hydride (Mg(AlH ₄ ) ₂ ), calcium aluminum hydride (Ca(AlH ₄ ) ₂ ), hydroboration Lithium (LiBH ₄ ), sodium borohydride (NaBH ₄ ), potassium borohydride (KBH ₄ ), bismuth borohydride (Be(BH ₄ ) ₂ ), magnesium borohydride (Mg(BH ₄ ) ₂ ), calcium borohydride ( A group consisting of Ca(BH ₄ ) ₂ ), lithium hydride (LiH), sodium hydride (NaH), magnesium hydride (MgH ₂ ), and calcium hydride (CaH ₂ ). As in the first embodiment, before the powder of the catalyst 200 is used for the hydride hydrolysis reaction, the powder of the catalyst 300 can be pulverized into particles having a size of about 1 μm to 10 mm to increase the total surface area. When it is used to catalyze the hydrolysis reaction of a hydride with water, the hydrogen generation can be further accelerated.

Hereinafter, a method of manufacturing the catalyst 300 of the present embodiment will be described with reference to a flowchart. Please refer to FIG. 6 and FIG. 7. FIG. 6 is a flow chart showing a method for manufacturing a catalyst according to a second embodiment of the present invention, and FIG. 7 is a schematic view showing a catalyst for manufacturing according to a second embodiment of the present invention. In the second embodiment, the catalyst 300 manufacturing method includes the following steps.

First, as shown in step S61, an aqueous solution containing a metal catalyst ion 320' is provided. Wherein, the aqueous solution is a metal salt aqueous solution, and the molar concentration of the metal catalyst ion 320' in the aqueous solution is required to be about 0.001 M to 10 M depending on the application.

Next, as shown in step S62, a plurality of catalyst carriers 310 are provided. Each of the catalyst carriers 310 has a plurality of chelating units 311. Similarly, in step S62, the catalyst carriers 310 may be pulverized into particles having a uniform size and a particle size ranging from 1 μm to 10 mm by means of polishing or the like.

Then, as shown in step S63, the catalyst carriers 310 are placed in an aqueous solution. In this step S63, the metal catalyst ions 320' in the aqueous solution are sequestered to the chelate unit 311 on the surface of each of the catalyst carriers 310.

Next, as shown in step S64, the metal catalyst ions 320' on the catalyst carrier 310 are reduced, so that the surface of the catalyst carrier 310 is covered with a plurality of gold The catalyst nanostructures 320 and/or a plurality of metal catalyst atoms are formed to form the catalyst 300.

Moreover, in this step S64, the present embodiment also proposes a method of reducing the metal catalyst ion 320' to provide a reference for those skilled in the art to implement. For example, in step S64, a reducing agent may be used to reduce the metal catalyst ions 320' to become metal catalyst atoms, wherein all of the metal catalyst atoms may form a plurality of metal catalyst nanostructures 320, Alternatively, only a portion of the metal catalyst atoms form a plurality of metal catalyst nanostructures 320, depending on the actual operating conditions. Please refer to FIG. 8 , which is a flow chart showing a method for reducing metal catalyst ions according to the present invention. The method of reducing metal catalyst ions 320' proposed herein includes the following steps. First, as shown in step S81, the catalyst carriers 310 having the surface chelated with the metal catalyst ions 320' are taken out. Next, as shown in step S82, the catalyst carriers 310 are washed to remove the unchelated metal catalyst ions 320'. Then, as shown in step S83, a reducing agent such as sodium borohydride, potassium borohydride, dimethylamino borane, hydrazine (N ₂ H ₄ ), formaldehyde, formic acid or sulfite is provided. An aqueous solution, and the molar concentration of the reducing agent is about 0.0001 M to 10 M depending on the application. Then, as shown in step S84, the catalyst carriers 310 are placed in a reducing agent, waiting for a reduction time. In step S84, the metal catalyst ions 320' on the surface of the catalyst carriers 310 are reduced to form a plurality of metal catalyst nanostructures 320 and/or a plurality of metal catalyst atoms. Moreover, the reduction time depends on the molar concentration of the reducing agent applied and the dose is about 5 seconds to 48 hours.

Then, as shown in step S65, the catalysts 300 are collected. Similarly, The method of collecting the catalyst 300 in this embodiment is similar to the first embodiment. In this step S65, the steps of taking out the catalysts 300, cleaning the catalysts 300, and drying the catalysts 300 are also included. Wherein, in the step of drying the catalyst 300, the catalyst 300 is also dried in a vacuum environment or in an inert gas.

Further, in the present embodiment, the operating temperature of the catalyst 300 is set to be between -20 ° C and 80 ° C. Therefore, this embodiment does not require the use of a high temperature system, but utilizes a chelation reaction and a reduction reaction to capture metal catalyst ions with an ion exchange resin and then reduce it to a metal catalyst nanostructure and/or a metal catalyst atom. Where the metal catalyst ion is reduced, it may be partially reduced to a metal catalyst atom, and the other portion may be reduced to a metal catalyst nanostructure. Depending on the reduction operating conditions, the present invention is not limited thereto. Compared with the conventional catalyst manufacturing method, the nano-metal catalyst of the present embodiment is relatively simple, and in addition to being fast and mass-produced, it has the advantages of low equipment cost and the permeable concentration. Time to control the chelation reaction and the reduction reaction to facilitate the overall production operation.

In the following, only one of the many preparation examples of the present invention will be described in detail as a reference for those skilled in the art. However, it is to be understood by those skilled in the art that the details of the elements and the details of the steps are not intended to limit the scope of the invention. In practical applications, the experimental parameters can be adjusted appropriately according to the needs of the application conditions.

Preparation example

In this example, a strong acid (cationic) ion exchange resin IR-120 is used as a catalyst carrier, and a noble metal ruthenium (Ru) is used as a metal catalyst. The cerium ion (Ru ³⁺ ) is first chelated to the surface of the ion exchange resin IR-120. The ruthenium ion (Ru ³⁺ ) on the surface of the resin IR-120 is reduced to a ruthenium atom (Ru) by a chemical reduction method using a strong reducing agent sodium borohydride (NaBH ₄ ) to produce a nano-structured ruthenium (Ru). The catalyst was applied to the surface of the resin IR-120.

The detailed steps of the catalyst preparation method of this example are as follows:

(a) 5 g of ruthenium chloride salt (RuCl ₃ ) was completely dissolved in 100 ml of deionized water to prepare an aqueous solution of ruthenium chloride. Wherein the concentration of the ruthenium ion molar ratio of about ^{0.24M, [Ru 3+] = 0.24M} .

(b) 20 g of IR-120 was placed in an aqueous solution of barium chloride and stirred at 150 rpm.

(c) over about 4 hours, IR-120 as a dark gradually changed, this has a number of representatives of ions of ruthenium (Ru ³⁺⁾ IR-120 chelated to a chelating group of the surface. The dark black IR-120 was removed and rinsed with a large amount of deionized water to remove unchelated strontium ions (Ru ³⁺ ).

(d) Calculate the weight of the ruthenium ion (Ru ³⁺ ) chelated on the surface of IR-120 by weighing, and prepare a sodium borohydride aqueous solution as a reducing agent according to a molar ratio of Ru:NaBH ₄ of 1:2. use. Among them, the weight of the ruthenium ion (Ru ³⁺ ) chelated on the surface of the IR-120 increases with the increase of the waiting time of the step (c). It is possible to control by the waiting time in step (c), the upper surface of the chelation controlled ruthenium ion (Ru ³⁺⁾ by weight of IR-120.

(e) IR-120 chelated with ruthenium ions (Ru ³⁺ ) was placed in an aqueous solution of sodium borohydride and stirred at 150 rpm.

(f) After about 3 hours, IR-120 gradually changed from dark black to bright silver, which means that a certain amount of ruthenium ions (Ru ³⁺ ) have been reduced to ruthenium atoms (Ru) on the surface of IR-120. Remove the bright silver IR-120 and rinse with plenty of deionized water.

(g) The IR-120 was placed in a vacuum oven and vacuum dried at 25-80 °C.

(h) After the IR-120 is dried, the catalyst preparation is completed.

After completion of the preparation of the catalyst, the properties of the catalyst and the catalytic catalytic hydrogen release reaction were tested. As a result of the property analysis of the catalyst, it was found that the surface of IR-120 has a plurality of granular ruthenium (Ru) nanostructures having an average particle diameter of about 60 to 80 nm. In addition, in the catalyst catalytic hydrogen evolution reaction test, the catalyst was prepared to catalyze the hydrolysis reaction of sodium borohydride with water to generate hydrogen gas, and the maximum hydrogen release rate was 3630 ml. Min ^-1 . g ^-1 .

The catalyst for catalytic hydrogen release reaction disclosed in the above embodiments of the present invention and the method for producing the same are characterized in that the chelate reaction and the reduction reaction are used to make the catalyst carrier surface have many metal catalyst ions or many nano-grade metals. catalyst. In addition to providing a high rate of hydrogen evolution, it has the advantages of not requiring the use of high temperature systems, low equipment costs, and rapid mass production to achieve commercialization goals. In the case of metal catalyst ions, the chelation reaction of the ion exchange resin can directly capture the metal catalyst ions on the surface thereof, and the concentration and time can be controlled to control the amount of chelation to facilitate the overall production operation. The second is the nano-scale metal catalyst, which can also pass the concentration and time. In order to control the chelation reaction and the reduction reaction, in order to facilitate the overall production operation.

In conclusion, the present invention has been disclosed in the above embodiments, but it is not intended to limit the present invention. A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

100, 200, 300‧‧‧ catalyst

110, 210, 310‧‧‧catalyst carrier

120‧‧‧Metal catalyst layer

220, 320'‧‧‧Metal Catalyst Ions

211, 311‧‧‧ Chelating

320‧‧‧Metal catalyst nanostructure

Figure 1 is a schematic view showing a catalyst for a conventional hydrogen evolution reaction.

Fig. 2 is a schematic view showing a catalyst for catalyzing a hydrogen evolution reaction according to a first embodiment of the present invention.

3 is a flow chart showing a method of manufacturing a catalyst according to a first embodiment of the present invention.

Figure 4 is a schematic view showing the manufacture of a catalyst according to a first embodiment of the present invention.

Fig. 5 is a schematic view showing a catalyst for catalyzing a hydrogen evolution reaction according to a second embodiment of the present invention.

FIG. 6 is a flow chart showing a method of manufacturing a catalyst according to a second embodiment of the present invention.

Figure 7 is a schematic view showing the manufacture of a catalyst according to a second embodiment of the present invention.

Figure 8 is a flow chart showing a method of reducing metal catalyst ions in accordance with the present invention.

Claims (8)

A method for catalyzing a hydrogen evolution reaction using a metal ion catalyst, wherein the metal ion catalyst comprises: a catalyst carrier of an ion exchange resin, the surface having a plurality of chelating groups; and a plurality of metal catalyst ions, respectively Chelating the chelating groups on the surface of the catalyst carrier, wherein the metal catalyst ions are selected from the group consisting of ruthenium (Ru), cobalt (Co), nickel (Ni), iron (Fe), manganese ( At least one metal catalyst ion in the group consisting of Mn) and copper (Cu). A method for catalyzing a hydrogen evolution reaction using a metal ion catalyst as described in claim 1, wherein the catalyst carrier has a particle diameter of from 1 μm to 10 mm. A method for catalyzing a hydrogen evolution reaction using a metal ion catalyst as described in claim 1, wherein the catalyst carrier is a cationic ion exchange resin. A method for catalyzing a hydrogen evolution reaction using a metal ion catalyst as described in claim 3, wherein the cationic ion exchange resin is selected from the group consisting of MSC-1B, DowEX-HCR-W2, MSC-1A, Amberlyst- 15. A group consisting of DowEX-22, DowEX-88, and IR-120. A method for catalyzing a hydrogen evolution reaction using a metal ion catalyst as described in claim 1, wherein the catalyst carrier is an anionic ion exchange resin. Use of metal ion catalyst as described in item 5 of the patent application A method for catalyzing a hydrogen evolution reaction, wherein the anionic ion exchange resin is selected from the group consisting of A-26, IRA-400, IRA-900, DowEX-550A, DowEX-MSA-1, DowEX-MSA-2, and A- A group of 36. The method for catalyzing a hydrogen evolution reaction using a metal ion catalyst as described in claim 1 is for catalyzing a hydrogen evolution reaction of a hydride with water. A method for catalyzing a hydrogen evolution reaction using a metal ion catalyst as described in claim 7 wherein the hydride is selected from the group consisting of lithium aluminum hydride (LiAlH ₄ ), sodium aluminum hydride (NaAlH ₄ ), aluminum magnesium hydride. _{(Mg (AlH 4) 2)} , calcium aluminum hydride _{(Ca (AlH 4) 2)} , lithium borohydride (LiBH _4), sodium borohydride (NaBH _4), potassium borohydride (KBH _4), borohydride beryllium (Be (BH ₄ ) ₂ ), magnesium borohydride (Mg(BH ₄ ) ₂ ), calcium borohydride (Ca(BH ₄ ) ₂ ), lithium hydride (LiH), sodium hydride (NaH), magnesium hydride (MgH ₂ ), And a group consisting of calcium hydride (CaH ₂ ).