JP6085331B2 - REAGENT COMPLEX AND METHOD FOR SYNTHESIZING REAGENT COMPLEX - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Cross-reference to related applications This application is a continuation-in-part of application number 14 / 046,081, filed October 4, 2013, and filed March 19, 2014 No. 14 / 219,823, each of which is hereby incorporated by reference herein in its entirety.

TECHNICAL FIELD The present invention relates generally to composites of zerovalent metal elements that are stably complexed with one or more hydride molecules, and more particularly to zerovalent manganese or tin complexed with lithium borohydride, and And a method for synthesizing the complex.

Background Hydrides, compounds in which metals or metalloids are bonded directly to hydrogen, are relatively active molecules with a wide variety of known and developing applications in chemical and energy technology. Such applications include applications as reducing agents, hydrogenation catalysts, desiccants, strong bases, components in rechargeable batteries, and possibly solid hydrogen storage media in fuel cell technology.

  Metal nanoparticles, i.e. pure or alloyed elemental metal particles with dimensions of less than 100 nm, have unique physical, chemical, electrical properties, compared to their corresponding bulk metals, Has magnetic properties, optical properties, and other properties. Therefore, these particles are used or developed in fields such as chemistry, medicine, energy and high performance electronic equipment, among others.

  Synthetic methods for metal nanoparticles are typically characterized by being “top-down” or “bottom-up”, with various chemical and physical approaches And even biological approaches. Top-down technology involves physically decomposing macroscale metal particles into nanoscale particles using various energy inputs. The bottom-up method involves forming nanoparticles from separated atoms, molecules or clusters.

  Physical force methods for top-down metal nanoparticle synthesis included comminution of macroscale metal particles, laser ablation of macroscale metal and electrical discharge machining of macroscale metal. A chemical approach to bottom-up synthesis generally involves reducing metal salts to zerovalent metal elements using nucleated seed particles or autonucleation and growing into metal nanoparticles.

Each of these methods may be effective in some situations, but may have disadvantages or become inapplicable depending on the situation. Direct grinding methods can limit the size of available particles (it is often difficult to produce particles smaller than 20 nm), and the stoichiometry of the alloy can become uncontrollable. Other physical methods can be costly or unacceptable on an industrial scale. On the other hand, chemical reduction techniques may not be useful, for example, in situations where metal cations are resistant to chemical reduction. Mn (II) is for example substantially not affected by the chemical reduction of in situ and therefore, it is impossible to apply this approach to the formulation or Mn ⁰ containing nanoparticles containing Mn ^0.

  Non-metallic nanoparticles have not been studied as well as metal nanoparticles, but techniques for synthesizing them have been developed in some circumstances. Similar to metal nanoparticles, non-metallic nanoparticles have spectroscopic and other properties that are substantially different from bulk elements, such as the fluorescence of carbon nanoparticles.

  It would be useful to have a single synthetic method that can produce high purity elemental nanoparticles of any composition, whether metal, metalloid or non-metal.

SUMMARY Compositions of zero-valent metal elements complexed with hydrides and methods for synthesizing the compositions are provided.

  In one aspect, a reagent complex is disclosed. The reagent complex includes a complex according to Formula I.

Q ⁰ · X _y I
Here, Q ⁰ is a zero-valent element, X is a hydride, and y is an integer or decimal value greater than 0. In some variations, the zero-valent element is non-metallic, while in other variations, the zero-valent element is a metal or metalloid. In two specific examples where the zerovalent element is non-metallic, it is selenium or carbon. In some cases, the hydride may be lithium borohydride and y may be 1 or 2.

  In another aspect, a method for synthesizing a reagent complex is disclosed. The method includes ball milling a mixture comprising both a hydride and a formulation containing a zero valent element. In different variations, the zero-valent element may be a non-metallic or metallic element and the hydride may be a composite metalloid hydride. In some specific examples, the zero-valent element is carbon or selenium and the hydride is lithium borohydride.

  In another aspect, a composition comprising a reagent complex synthesized by a method comprising ball milling a mixture comprising both a hydride and a formulation containing a zero valent element is provided.

BRIEF DESCRIPTION OF THE DRAWINGS Various aspects and advantages of the present invention will become apparent and more readily appreciated from the following description of embodiments read in conjunction with the accompanying drawings, in which:

It is a diagram showing a boron X-ray photoelectron spectrum of LiBH _4. Is a diagram showing a boron X-ray photoelectron spectra of Mn · LiBH ₄ complexes synthesized by the disclosed methods for synthesizing reagent complex. Is a diagram showing a boron X-ray photoelectron spectra of Mn · (LiBH _{4) 2} complexes synthesized by the disclosed methods for synthesizing reagent complex. It is a diagram illustrating a manganese X-ray photoelectron spectra of Mn ⁰ powder. It is a diagram illustrating a manganese X-ray photoelectron spectra of Mn · (LiBH _{4) 2} complexes synthesized by the disclosed methods for synthesizing reagent complex. Is a diagram showing a superposition of the Mn · X-ray photoelectron spectrum of (LiBH _{4) 2} complex of Mn ⁰ powder X-ray photoelectron spectra and 2B of Figure 2A. FIG. 4 shows an X-ray powder diffraction scan of a Mn · LiBH ₄ complex synthesized by the disclosed method for synthesizing a reagent complex. FIG. 4 shows an X-ray powder diffraction scan of a Mn. (LiBH ₄ ) ₂ complex synthesized by the disclosed method for synthesizing a reagent complex. FIG. 3 shows superposition of FT-IR spectra of Mn · LiBH ₄ complex synthesized by the method of FIG. 1 and Mn · (LiBH ₄ ) ₂ complex synthesized by the disclosed method for synthesizing a reagent complex. FIG. It is a diagram showing a tin X-ray photoelectron spectrum of the sn ⁰ powder. It is a diagram illustrating a Sn · (LiBH _{4) 2} Tin X-ray photoelectron spectrum of the complexes synthesized by the disclosed methods for synthesizing reagent complex. Is a diagram showing a superposition of the Sn · X-ray photoelectron spectrum of (LiBH _{4) 2} complex of Sn ⁰ powder X-ray photoelectron spectra and 5B in Figure 5A. W is a diagram showing an X-ray photoelectron spectrum of ⁰ powder. It shows an X-ray photoelectron spectrum of the W · (LiBH _{4) 2} complexes synthesized by the disclosed methods for synthesizing reagent complex. Is a diagram showing a superposition of the W · X-ray photoelectron spectrum of (LiBH _{4) 2} complexes of ^{W 0} powder X-ray photoelectron spectra and 6B in Figure 6A. La is a diagram showing an X-ray photoelectron spectrum of ⁰ powder. It shows an X-ray photoelectron spectrum of the La · (LiBH _{4) 2} complexes synthesized by the disclosed methods for synthesizing reagent complex. It is a diagram showing a superposition of the X-ray photoelectron spectrum of the La · (LiBH _{4) 2} complex of La ⁰ powder X-ray photoelectron spectra and 7B in Figure 7A. Ge is a diagram showing an X-ray photoelectron spectrum of ⁰ powder. Shows an X-ray photoelectron spectrum of Ge · (LiBH _{4) 2} complexes synthesized by the disclosed methods for synthesizing reagent complex. Figure 8 A Ge ⁰ powder X-ray photoelectron spectra and FIG. 8 Ge · (LiBH ₄₎ in B in a diagram showing the superimposition of X-ray photoelectron spectrum of the ₂ complex. It shows an X-ray photoelectron spectra of Se · (LiBH _{4) 2} complexes synthesized by the disclosed methods for synthesizing reagent complex. It shows an X-ray photoelectron spectrum of the C · (LiBH _{4) 2} complexes synthesized by the disclosed methods for synthesizing reagent complex.

DETAILED DESCRIPTION The chemical compositions provided herein can have substantial utility in the “wet chemistry” synthesis of high purity elemental nanoparticles. Suitable reagents for synthesizing metal nanoparticles, metalloid nanoparticles or non-metal nanoparticles are disclosed. The disclosed method for formulating chemical compositions is simple and reproducible. Further, as disclosed herein, the method can generate reagents that incorporate any of a wide range of elements. The elements or “zero valent” elements incorporated into the disclosed chemical compositions substantially comprise any solid element, whether metal, metalloid or non-metal.

  The chemical compositions of the present disclosure generally include a zero valent element complexed with a hydride molecule. These compositions can be formulated by utilizing the disclosed method, which generally includes the operation of ball milling the elemental material with the hydride.

  “Zerovalent” or “zerovalent element” as used herein refers to the state in oxidation state 0. The term may alternatively be defined as representing a state that is neither ionized nor covalently associated with other species. More generically, the phrase “zero valent” as used herein refers to the state of the material as expressed in elemental form.

  The term “element” as used herein refers to any element of the periodic table in the zero-valent form. In particular, in its zero-valent form, it refers to any element that is solid under the conditions of use. Even more particularly, the term “element” as used herein refers to any element that is a solid under standard temperature and pressure conditions.

  The phrase “metal element” refers to a metal, lanthanide or metalloid. “Metal” may refer to alkaline earth metals, alkali metals, transition metals, or post-transition metals. The term “transition metal” may refer to any D-block metal from Groups 3-12. The term “post-transition metal” may refer to a Group 13-16 metal. The term “metalloid” may refer to any of boron, silicon, germanium, arsenic, antimony, tellurium, or polonium.

  As used herein, the phrases “non-metallic element” and “non-metallic” refer to any non-metallic element, particularly any non-metallic element that is generally solid under standard conditions of temperature and pressure. In particular, the phrases “non-metallic element” and “non-metallic” refer to any of carbon, phosphorous acid, sulfur, and selenium.

As used herein, the term “hydride” generally refers to any molecular species that can function as a hydrogen anion donor. In different examples, the hydride referred to herein is a two-element metal hydride (eg, NaH or MgH ₂ ), a two-element metalloid hydride (eg, BH ₃ ), a complex metal hydride (eg, LiAlH ₄ ), or a complex metalloid hydrogen. It may be halides (e.g. LiBH ₄ or _{Li (CH 3 CH 2) 3} BH). In some examples, the hydride will be LiBH ₄ . The term hydride described above may in some variations include the corresponding deuteride or tritide. A reagent complex comprising a complex according to Formula I is disclosed.

Q ⁰ · X _y I
Here, Q ⁰ is a zero-valent element, X is a hydride, and y is an integer or decimal value greater than 0. In some variations, the zero-valent element Q ⁰ can be non-metallic, and in other variations, it can be a metallic element.

For example, in some variations, the reagent complex comprises a complex according to Formula II.
D ⁰ · X _y II
Here, D ⁰ is a zero-valent nonmetallic element, X is a hydride, and y is an integer value or a decimal value larger than 0. In other variations, the reagent complex further comprises a complex according to Formula III.

E ⁰・ X _y III
Here, E ⁰ is a zero-valent metal element, X is a hydride, and y is an integer or decimal value greater than 0. Thus, it should be understood that Formulas II and III are of the Formula I type.

  In one more specific variation of a reagent complex comprising a complex according to Formula III, the metal element can be a metal and the reagent complex can be represented by Formula IV.

M ⁰ · X _y IV
Here, M ⁰ is a zero-valent metal, X is a hydride, and y is an integer or decimal value greater than 0. Thus, it should be understood that Formula IV is a type of Formula III.

  The value y according to Formula I may define the stoichiometric ratio of hydride molecules to zero-valent element atoms in the reagent complex. The value of y can include any integer or decimal value greater than zero. In some cases, a 1: 1 stoichiometric ratio where y equals 1 may be useful. In some cases, it may be preferred that the hydride is in molar excess with respect to the zero-valent element, for example y equals 2 or 4. The molar excess of hydride relative to the zero-valent element can in some cases ensure that there is sufficient hydride for subsequent use.

  The reagent complex of the present disclosure may have an arbitrary supramolecular structure or may not have a supramolecular structure. No structural details are suggested by any of formulas I-IV. While not being restricted or limited to a particular structure, the reagent complex may exist as a supramolecular cluster of many zero-valent element atoms interspersed with hydride molecules. The reagent complex may exist as a cluster of zero-valent element atoms whose clusters are surface coated with hydride molecules. Reagent complexes may exist as individual zero-valent element atoms that have little or no molecular assembly with each other, but each is associated with a hydride molecule according to Formula I. All of these optical tissues, or any other consistent with Formula I, are intended to be within the scope of this disclosure.

  A method for synthesizing reagents includes ball milling a mixture containing both a hydride and a formulation containing a zero valent element. The resulting reagent, alternatively referred to herein as a reagent complex, includes a complex according to Formula I.

Q ⁰ · X _y I
Here, Q ⁰ is at least one atom obtained from a preparation containing a zero-valent element in the oxidation state 0, X is a hydride molecule, and y is an integer or decimal value greater than 0. is there.

  In different variations of the method, the zero-valent element can be a non-metallic or metallic element. In some variations of the latter, the zero valent element can be a metal. Thus, the reagent complex resulting from the ball milling step can more specifically include a complex according to any of Formulas II-IV.

D ⁰ · X _y II
E ⁰・ X _y III
M ⁰ · X _y IV
Here, D ⁰ is at least one non-metallic atom obtained from a formulation containing a zero-valent non-metal in the oxidation state 0, and E ⁰ is a formulation containing a zero-valent metal element in the oxidation state 0 At least one atom of the metal element obtained from the product, M ⁰ in the oxidation state 0 is at least one metal atom obtained from the formulation containing a zerovalent metal, and X and y are defined above Street.

  Regardless of whether the zero-valent element is a non-metal, a metal element or a metal, the formulation containing the zero-valent element may be any composition consisting essentially of the zero-valent element. In many cases, formulations containing zero valent elements will contain zero valent elements in a form having a high surface area to mass ratio. In some cases, the zero-valent element will be present in powder form with a particle size of -325 mesh. It is contemplated that the formulation containing a zero valent element can be a highly porous zero valent element, a zero valent element with a honeycomb structure, or some other formulation having a high surface to mass ratio.

  The phrase “high surface area to mass ratio” can encompass a wide range of surface area to mass ratios, and generally the surface area to mass ratio of the formulation containing the zero valent element employed will synthesize the reagent. It is contemplated that it may be necessary due to the time constraints of the method to do. In general, the higher the surface area to mass ratio of a formulation containing a zerovalent element, the faster the method for synthesizing the reagent will be completed. If a formulation containing a zero valent element is made of a zero valent element powder, the smaller the particle size of the zero valent element powder, the faster the method for synthesizing the reagent will be completed. Let's go.

  In some variations of the method for synthesizing the reagents, the hydride and the formulation containing the zero valent element are included in the formulation containing the hydride molecule and the zero valent element during the ball milling step. There may be a 1: 1 stoichiometric ratio with the metal atom. In other variations, the stoichiometric ratio may be 2: 1, 3: 1, 4: 1 or more. In some variations, the stoichiometric ratio of hydride molecules to elemental metal atoms in a formulation containing a zero valent element may also include a fraction such as 2.5: 1.

  Referring now to FIGS. 1-9, the following spectroscopic data illustrates some properties of the reagent complexes of the present disclosure. In some cases, the spectroscopic data also illustrates properties of exemplary materials that can be used in methods for synthesizing reagent complexes. In all cases, the reagent conjugates were formulated by the disclosed method for synthesizing the reagent conjugates.

FIG. 1A shows an x-ray photoelectron spectroscopy (XPS) scan in the boron region of hydride (LiBH ₄ ) that has not been incorporated into the reagent complex. 1B and 1C show similar boron XPS scans of Mn · LiBH ₄ and Mn · (LiBH ₄ ) ₂ , respectively. A thick solid line indicates raw XPS data, and a thin solid line indicates adjusted data. Dashed lines and / or dotted lines indicate individual deconvoluted peaks. Uncombined LiBH ₄ in FIG. 1A shows two large peaks centered at 191.60 eV and 187.25 eV and two smaller peaks centered at 190.21 eV and 185.92 eV.

Here, when FIG. 1B is compared with FIG. 1A, three of the boron peaks are virtually eliminated by ball milling LiBH ₄ with an equimolar amount of a formulation containing zerovalent manganese. Only the peak centered at is left. It can be seen that the change in the boron XPS spectrum of LiBH ₄ occurs by ball milling with a zero valent element formulation, indicating that a complex according to Formula I has been formed. As can be seen from the comparison with FIG. 1C, a boron peak centered at 189.92 eV appears again by ball milling LiBH ₄ with a two-fold molar excess of zero-valent manganese instead of an equimolar amount. . This may indicate that part of LiBH ₄ is not complexed.

FIG. 2A shows an XPS scan of manganese powder. FIG. 2B shows an XPS scan of the manganese region of Mn. (LiBH ₄ ) ₂ . A thick solid line indicates raw XPS data, and a thin solid line indicates adjusted data. Dashed lines and / or dotted lines indicate individual deconvoluted peaks. As seen in FIG. 2A, the spectrum of manganese powder includes two broad peaks, each of which consists of three component peaks that are observable after deconvolution. Referring now to FIG. 2A and focusing on the spectral region of ˜639 eV to 642 eV, the three component peaks for manganese powder are based on published references, manganese oxide species (640.52 eV and 641.90 eV). ) As well as zero-valent manganese (639.05 eV). The ball milled reagent complex represented in FIG. 2B lost the oxide peak at 641.90 eV but maintained the oxide peak (the peak at 640.77 eV in FIG. Considered the same as the 640.52 eV peak). The ball milled reagent complex also maintains a zerovalent manganese peak at 639.05 eV (after a slight change).

An important point in the spectrum of FIG. 2B is that the ball milled reagent complex exhibits a new phase at the component peaks at 637.75 eV and 636.06 eV. These latter two can be assigned to manganese combined with hydride. An overlay of the manganese XPS data obtained for the manganese powder and ball milled Mn. (LiBH ₄ ) ₂ reagent complex is shown in FIG. 2C. This comparison illustrates the disappearance of at least one manganese oxide species and the emergence of a new phase, resulting in a change to an overall lower electronic binding energy.

3A and 3B show the XRD spectra of the Mn · LiBH ₄ and Mn · (LiBH ₄ ) ₂ reagent complexes of FIGS. 1B and 1C. Both diffraction analyzes suggest that the sample is primarily amorphous, as indicated by the lack of an overall peak. A small peak consistent with 20 nm manganese metal is observed, but no peak consistent with LiBH ₄ or manganese oxide appears.

An overlay of FT-IR scans for the reagent complexes Mn · LiBH ₄ and Mn · (LiBH ₄ ) ₂ is shown in FIG. Both spectra ^are, BH ₄ ^- 2299cm -1 corresponding to the IR active mode, with a remarkable feature in 1230 cm ^-1 and 1092cm ^-1. This result suggests that the tetrahedral structure of BH ₄ ⁻ remains essentially unchanged by incorporating LiBH ₄ into the reagent complex.

FIG. 5A shows an XPS scan of tin powder. FIG. 5B shows the corresponding XPS scan of the reagent complex Sn · (LiBH ₄ ) ₂ synthesized therefrom. Two large peaks at 495.14 eV and 486.72 eV and two small peaks at 493.18 eV and 485.03 eV (FIG. 5A) in the tin powder data are substantially different in the reagent complex (FIG. 5B) and / Or disappear. At these positions, the reagent complex Sn · (LiBH ₄ ) ₂ has large peaks at 492.30 eV and 483.80 eV, and small peaks at 495.53 eV, 494.00 eV, 487.25 eV and 485.69 eV. (FIG. 5B).

An overlay of the adjusted XPS data for the tin powder and the corresponding Sn. (LiBH ₄ ) ₂ reagent complex is shown in FIG. 5C. This comparison also shows that the incorporation of tin into the reagent complex occurs concomitantly with the spectral shift to lower electronic binding energy in the tin region XPS.

Referring now to FIGS. 6A and 6B, XPS spectra for tungsten composited with tungsten powder and LiBH ₄ are shown, respectively. The resulting spectrum is represented by a solid line and the fitted component peaks are indicated by various dashed and dotted lines. FIG. 6C shows a superposition of W and the W · (LiBH ₄ ) ₂ spectrum. As evidenced by the results in FIG. 6C, complex formation of W ⁰ with LiBH ₄ leads to lower binding energies of the valence electrons of the metal elements, as in the above case for Mn ⁰ and Sn ⁰ . Associated with changes.

Referring now to FIGS. 7A and 7B, XPS spectra for lanthanum powder and reagent complex La. (LiBH ₄ ) ₂ are shown, respectively. FIG. 7C shows a superposition of the resulting spectra of FIGS. 7A and 7B.

XPS spectra for the germanium powder and the Ge · (LiBH ₄ ) ₂ reagent complex are shown in FIGS. 8A and 8B, respectively. The resulting spectral overlay is shown in FIG. 8C. In addition, although the previous data was about various metals, the data of FIG. 8A-FIG. 8B show complex formation when a zerovalent element is a metalloid. The change to lower electron binding energy after complex formation is similar to that observed previously.

9A and 9B show comparable XPS spectra for two representative reagent complexes where the zero valent element is non-metallic. The Se · (LiBH ₄ ) ₂ complex has peaks centered around 56.58 eV, 55.54 eV, 54, 31 eV, and 53.34 eV, and the C · (LiBH ₄ ) ₂ spectrum is about 286. It has peaks centered at 79 eV, 285.39 eV, 284.73 eV, and 283.64 eV. These results support the applicability of the method to non-metallic elements.

Also disclosed are reagent complexes comprising complexes according to Formula I.
Q ⁰ · X _y I
Here, Q ⁰ is a zero-valent element, X is a hydride, and y is an integer or decimal value greater than 0. The reagent complex is formulated by a method for synthesizing the reagent complex comprising ball milling a mixture comprising both a hydride and a formulation containing a zero valent element.

  In different variations of reagent complexes prepared by the method, in different variations of the method, the zero-valent element can be a non-metal or a metallic element. In some variations of the latter, the zero valent element can be a metal. Therefore, the reagent complex prepared by the method may more specifically include a complex according to any of Formula II to Formula IV.

D ⁰ · X _y II
E ⁰・ X _y III
M ⁰ · X _y IV
Here, D ⁰ is at least one non-metallic atom obtained from a formulation containing a zero-valent non-metal in the oxidation state 0, and E ⁰ is a formulation containing a zero-valent metal element in the oxidation state 0 At least one atom of the metal element obtained from the product, M ⁰ in the oxidation state 0 is at least one metal atom obtained from the formulation containing a zerovalent metal, and X and y are defined above Street.

  In various aspects, a hydride as prepared by the method and incorporated into a reagent complex is any hydrogen, including a two-element metal hydride, a two-element metalloid hydride, a complex metal hydride, or a complex metalloid hydride. It may be a compound. In some variations, the hydride may be a complex metalloid hydride. In some cases, the hydride may be borohydride. In some cases, the hydride may be lithium borohydride.

  The value y according to Formula I may define the stoichiometric ratio of hydride molecules to zero-valent element atoms in the reagent complex. The value of y can include any integer or decimal value greater than zero. In some cases, y may be an integer value of 4 or less or a decimal value. In some cases, y may be an integer value or a decimal value of 2 or less. In some cases, y may be an integer value of 1 or less or a decimal value.

  The preparation containing a zero-valent element may be any composition substantially consisting of a zero-valent element. In many cases, formulations containing zero valent elements will contain zero valent elements in a form having a high surface area to mass ratio. In some cases, the zero-valent element will be present in powder form with a particle size of -325 mesh. It is contemplated that the formulation containing a zero valent element can be a highly porous zero valent element, a zero valent element with a honeycomb structure, or some other formulation having a high surface to mass ratio.

  The invention is further illustrated with reference to the following examples. It should be understood that these examples are provided to illustrate specific embodiments of the present invention and should not be construed as limiting the scope of the invention.

Example 1
1 part manganese metal powder with -325 mesh particle size is mixed with 1 part or 2 parts LiBH ₄ with a total mass of manganese metal and lithium borohydride powder of less than 10 grams, 1 ( 3/4 ) In a 250 mL stainless steel hermetic ball mill jar using an inch, 3 ( 1/2 ) inch and 5 ( 1/4 ) inch 316 stainless steel ball bearings (using a planetary ball mill with a Fritsch pullersetet 7) at 4 rpm Ball mill with planetary ball mill for time.

Example 2
1 part tin metal powder with -325 mesh particle size is mixed with 1 part or 2 parts LiBH ₄ with a total mass of tin metal and lithium borohydride powder of less than 10 grams, 1 ( 3/4 ) In a 250 mL stainless steel hermetic ball mill jar using an inch, 3 ( 1/2 ) inch and 5 ( 1/4 ) inch 316 stainless steel ball bearings (using a planetary ball mill with a Fritsch pullersetet 7) at 4 rpm Ball mill with planetary ball mill for time.

Example 3
Tungsten powder and lithium borohydride powder are added to a stainless steel ball mill under argon using a steel ball in a 1: 2 stoichiometric ratio. This mixture is then ground in a planetary ball mill for 4 hours at 150-400 rpm (depending on the hardness of the metal).

Example 4
Lanthanum powder and lithium borohydride powder are added to a stainless steel ball mill under argon using a steel ball in a 1: 2 stoichiometric ratio. This mixture is then ground in a planetary ball mill for 4 hours at 150-400 rpm (depending on the hardness of the metal).

Example 5
Germanium powder and lithium borohydride powder are added to a stainless steel ball mill under argon using a steel ball in a 1: 2 stoichiometric ratio. This mixture is then ground in a planetary ball mill for 4 hours at 150-400 rpm (depending on the hardness of the metal).

Examples 6-7
Lithium borohydride powder is added together with selenium or carbon powder in a 2: 1 stoichiometric ratio using a steel ball to a stainless steel ball mill under argon. This mixture is then ground in a planetary ball mill for 4 hours at 150-400 rpm (depending on the hardness of the metal).

The above description relates to what is currently considered the most practical embodiment. However, the disclosure should not be limited to these embodiments, but rather is intended to encompass various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Thus, it should be understood that this scope is to be construed most broadly to include all modifications and equivalent arrangements that are possible under law.

Claims (20)

The following formula:
Q ⁰・ Xy
(In the above formula, Q ⁰ is a zero-valent nonmetal in oxidation state 0, and X is a hydride containing at least one of a two-element metalloid hydride, a composite metal hydride, and a composite metalloid hydride. And y is an integer or decimal value greater than 0)
A reagent complex comprising a complex having: The following formula:
Q ⁰・ Xy
(In the above formula, Q ⁰ is a zero-valent non-metal, X is a hydride, and y is an integer or decimal value greater than 0)
A reagent complex comprising a complex having: The reagent complex according to claim 2, wherein Q ⁰ is a zero-valent nonmetal other than carbon.   The reagent complex according to claim 2, wherein the nonmetal is carbon or selenium.   The reagent complex of claim 2, wherein the non-metal is selenium. Q ⁰ is a zero-valent non-metal containing Selector down, reagent complex according to claim 1.   The reagent complex of claim 1, wherein the hydride comprises borohydride.   The reagent complex of claim 1, wherein the hydride comprises lithium borohydride.   The reagent complex according to claim 1, wherein y is 4 or less. A method for synthesizing a reagent complex comprising:
Ball milling a mixture containing both a hydride containing at least one of a two-element metalloid, a composite metal hydride, and a composite metalloid hydride and a preparation containing a zero-valent nonmetal in an oxidation state of 0 Steps,
The following formula:
Q ⁰・ Xy
(In the above formula, Q ⁰ is a zero-valent nonmetal in oxidation state 0, and X is a hydride containing at least one of a two-element metalloid hydride, a composite metal hydride, and a composite metalloid hydride. And y is an integer or decimal value greater than 0)
Synthesizing a reagent complex having: Q ⁰ is a zero-valent non-metal containing Selector down method of claim 10.   The method of claim 10, wherein the hydride comprises borohydride.   The method of claim 10, wherein the hydride comprises lithium borohydride. 11. The method of claim 10, wherein the hydride is mixed with a formulation containing a zero valent non-metal in a molar excess of 4 times or less.   The ball milling step is performed at 400 rpm in a stainless steel hermetic ball mill jar using 1 (3/4) inch, 3 (1/2) inch and 5 (1/4) inch 316 stainless steel ball bearings, The method according to claim 10, wherein the method is carried out on a planetary ball mill for 4 hours.   11. The method of claim 10, wherein the method is performed in an anoxic environment, in an anhydrous environment, or in an anoxic and anhydrous environment. A method for synthesizing a reagent complex comprising:
Ball milling a mixture comprising both a hydride and a formulation containing a zerovalent non-metal.   The method of claim 17, wherein the formulation containing a zero-valent nonmetal is a formulation containing a zero-valent nonmetal other than carbon.   The method of claim 17, wherein the formulation containing a zerovalent nonmetal is a formulation containing carbon or selenium.   20. The method of claim 19, wherein the formulation containing a zerovalent non-metal is a formulation containing selenium.

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