Applications of nanocatalytic systems and hydrogen transfer from solid-state storage

Abstract

This invention relates to metal nanoparticles stabilized by metallocene ligands. Nanoparticles and nanoparticle networks having a controlled microsize of 10 nm or less are used to efficiently and rapidly supply hydrogen gas (H2) extracted from solid organic raw materials in hydrolysis and solvation reactions, and are also recycled.

Description

[Technical Field]

[0001] The present invention relates to nanoparticles stabilized with ditopic and polytopic metallocene ligands, networks of these nanoparticles, and their use for delivering hydrogen (H2) from a chemical solid storage using amine boranes. [Background technology]

[0002] France aims to achieve carbon neutrality by 2050 (Energy and Climate Law No. 2019-1147, dated November 8, 2019). Among the targets set by the government, there is a focus on developing hydrogen solutions for the future energy mix.

[0003] Existing hydrogen storage solutions are in gaseous and / or liquid form. However, there are risks associated with hydrogen-related accidents, such as fires and explosions. Therefore, specific regulations have been created regarding the conception and use of hydrogen storage and hydrogen distribution resorts.

[0004] Furthermore, storing hydrogen in gaseous or liquid form requires enormous storage capacity.

[0005] Therefore, there is a need to develop safer and more economical hydrogen storage routes, not only in relation to transportation and mobility applications, but also in terms of social acceptance.

[0006] The chemical storage of hydrogen in solid form represents a safe and clean energy vector. For example, the storage of H2 as a solid in the form of amine boranes is known. However, there is a need to provide a method for the controlled and safe delivery of H2 via solid pathways. There is also a need for a renewable, cost-effective method that can deliver large quantities of H2 in a short time. [Prior art documents] [Patent Documents]

[0007]

Patent Document 1

Patent document 2

Patent document 3

Non-licensed literature

[0008] [Non-licensed document 1] Smaliy, RV, Beauperin, M., Cattey, H., Meunier, P., Hierso, J.-C., Roger, J., Doucet, H., Coppel, Y. Conformational Control of Metallocene Backbone by Cyclopentadienyl Ring Substitution: A New Concept in Polyphosphane Ligands Evidenced by “Through-Space” Nuclear Spin-Spin Coupling. Application in Heteroaromatics Arylation by Direct CH Activation. Organometallics 2009, 28, 3152-3160; FR 3014871; [Non-licensed document 2] Highly Functionalized Ferrocenes. Lerayer, E.; Radal, L.; Nguyen, T.-A.; Dwadnia, N.; Cattey, H.; Amardeil, R.; Pirio, N.; Roger, J.; Hierso, J.-C. European Journal of Inorganic Chemistry (2020), 419-445 [Non-licensed document 3] Smaliy, RV; Beauperin, M.; Cattey, H.; Meunier, P.; Hierso, J.-C.; Roger, J.; Doucet, H.; Coppel, Y. "Conformational control of metallocene skeletons by cyclopentadienyl ring substitution: A novel concept of polyphosphane ligands demonstrated by trans-spatial nuclear spin-spin coupling. Application to heteroaromatic arylation by direct CH activation." Organometallics 2009, 28, 3152-3160; FR 3014871; [Non-Patent Document 4] Highly Functionalized Ferrocenes. Lerayer, E.; Radal, L.; Nguyen, T.-A.; Dwadnia, N.; Cattey, H.; Amardeil, R.; Pirio, N.; Roger, J.; Hierso, J.-C. European Journal of Inorganic Chemistry (2020), 419-445 (Non-patent Document 4) [Overview of the project] [Problems that the invention aims to solve]

[0009] The present invention relates to metal nanoparticles stabilized by a metallocene ligand, wherein each 5-membered ring of the metallocene is -(CH2)n-XR 2 R 3 And in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, preferably 0. X is a metallic coordination atom, preferably P, N, B, or Al, preferably P, N, or B, preferably P or N, preferably P. R 2 and R 3 These may be the same or different, C5~C 10 An aryl group, preferably a phenyl group; C5~C 10A cycloalkyl group, preferably cyclohexyl; a 5- to 10-membered heteroaryl containing 1 or 2 heteroatoms, preferably O or N, which may optionally be substituted, for example, with a linear or branched C1-C5 alkyl group, such as a furyl group; a 5- to 10-membered heterocyclic ring containing 1 or 2 heteroatoms, preferably O or N; or a linear or branched, saturated or unsaturated C1-C 30 , preferably C1-C 10 alkyl, more preferably a C1-C5 alkyl group; preferably, R 2 and R 3 are the same or different and represent phenyl, cyclohexyl, isopropyl, tert-butyl or furyl; or R 2 and R 3 together with X, preferably when X is P, may contain 1 heteroatom selected from O, N, S, preferably N, and may optionally be substituted, for example, with a linear or branched C1-C5 alkyl group and / or N(linear or branched C1-C5 alkyl group)2 to form a 5- to 10-membered ring heterocycle -(CH2)n-XR 2 R 3 and -(CH2) n -COOR, wherein n is 0, 1, 2, 3 or 4, preferably 0 or 1, more preferably 0; R may be the same or different and is H; a C5-C 10 aryl group, preferably a phenyl group; a C5-C 10 cycloalkyl group, preferably a cyclohexyl group; or a linear or branched, saturated or unsaturated C1-C 30 , preferably C1-C 10 alkyl, more preferably a C1-C5 alkyl group; preferably, R is H for -(CH2) n -COOR and -(CH2) n COR, wherein n is 0, 1, 2, 3 or 4, preferably 0 or 1, more preferably 0; R may be the same or different, H;C5~C 10 Aryl group, preferably phenyl group; straight or branched, saturated or unsaturated C5-C 10 Cycloalkyl groups, preferably cyclohexyl groups; or C1-C 30 Preferably C1~C 10 Alkyl, more preferably C1-C5 alkyl; preferably R is H-(CH2) n COR and, -(CH2) n CONR 4 R 5 And in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, preferably 0; R 4 and R 5 These may be the same or different, H, C5~C 10 Aryl group, preferably phenyl group); C5-C 10 Cycloalkyl groups, preferably cyclohexyl groups, or linear or branched, saturated or unsaturated C1-C groups. 30 Preferably, C1-C 10 Alkyl, more preferably C1-C5 alkyl, or R 4 and R 5 It can combine with N atoms to form a 5-10 membered heterocycle, preferably R 4 and R 5 H is H - (CH2) n CONR 4 R 5 It is replaced by at least one identical or different group selected from the group consisting of and However, at least one of the five-membered rings of the metallocene must contain at least one (CH2) n -PR 2 R 3 It is substituted by the group, Each of the five-membered rings of metallocene may be the same or different, and the formula is CR 6 One or more, preferably one R selected from the group consisting of 3 groups 1 It may be substituted with, and in the formula, R 6C1-C is linear or branched, saturated or unsaturated. 30 Alkyl, preferably C1-C 10 Alkyl, more preferably C1-C5 alkyl, and optionally containing at least one heteroatom, preferably O or N; the following formula R 7 -C(CH3)2 is a gem-dimethyl group, and in the formula, R 7 C1-C is linear or branched, saturated or unsaturated. 30 Alkyl, preferably C1-C 10 Alkyl, more preferably C1-C5 alkyl, and optionally containing at least one heteroatom, preferably O or N; The metal of the metallocene is selected from the group consisting of Fe, Ni, Co, Cr, V, Rh, Ru, Os, and Re, and is preferably Fe; the atomic ratio of the nanoparticle metal to the metal of the metallocene is 5 / 1 or more, preferably 5 / 1 to 20 / 1, and preferably 10 / 1 to 20 / 1.

[0010] Preferably, the metal of the nanoparticles is ruthenium, nickel, platinum, rhodium, or cobalt, preferably ruthenium or nickel, preferably nickel, and preferably ruthenium.

[0011] According to the embodiment, the ligand of the present invention is -(CH2) n -XR 2 R 3 And: n is 0 or 1, preferably 0; X is P or N, preferably P; R 2 and R 3 These are either the same or different, C5-C 10 An aryl group, preferably a phenyl group; C5-C 10 Cycloalkyl groups, preferably cyclohexyl groups; or C1-C 30 Preferably, C1-C 10Alkyl, more preferably C1-C5 alkyl, linear or branched, saturated or unsaturated; preferably, R 2 and R 3 -(CH2) represents phenyl or cyclohexyl, either identical or different. n -XR 2 R 3 and, -(CH2) n -COOR, n is either 0 or 1, preferably 0; R is H, either identical or different; C5-C 10 An aryl group, preferably a phenyl group; C5-C 10 Cycloalkyl group, preferably cyclohexyl group; or C1-C 30 Preferably C1-C 10 Alkyl, more preferably C1-C5 alkyl, linear or branched, saturated or unsaturated, preferably R is H -(CH2) n -COOR and, -(CH2) n CONR 4 R 5 And, n is 0 or 1, preferably 0. R 4 and R 5 These are the same or different, H, C5-C 10 An aryl group, preferably a phenyl group, C5-C 10 Cycloalkyl groups, preferably cyclohexyl groups, or C1-C 30 Preferably, C1-C 10 Alkyl, more preferably C1-C5 alkyl, linear or branched, saturated or unsaturated, preferably R 4 and R 5 H is H - (CH2) n CONR 4 R 5 Selected from the group consisting of and .

[0012] Preferably, the metal of the metallocene is Fe.

[0013] According to an embodiment, the metallocene is selected from compounds having the following formula (I), (II) or (III),

[0014]

Chemical formula

[0015] wherein: n is 0 or 1, Z is: -(CH2) n -XR 2 R 3 and is R 2 and R 3 are the same or different and are a C5-C 10 aryl group, preferably phenyl; a C5-C 10 cycloalkyl group, preferably cyclohexyl; a 5- to 10-membered heteroaryl containing 1 or 2 heteroatoms, preferably O or N, optionally substituted, for example, by a linear or branched C1-C5 alkyl group, for example furyl; a 5- to 10-membered heterocycle containing 1 or 2 heteroatoms, preferably O or N; or a linear or branched, saturated or unsaturated C1-C 30 , preferably C1-C 10 alkyl group, more preferably a C1-C5 alkyl group, preferably R 2 and R 3 are the same or different and represent phenyl, cyclohexyl, isopropyl, tert-butyl or furyl, or R 2 and R 3 together with X, preferably when X is P, form a 5- to 10-membered heterocycle containing 1 heteroatom selected from O, N, S, preferably N, optionally substituted, for example, by a linear or branched C1-C5 alkyl group and / or N(linear or branched C1-C5 alkyl group)2 and may be -(CH2) n -XR 2 R 3 and -(CH2) n -COOR, wherein in the formula R may be the same or different, H;C5-C 10 Aryl group, preferably phenyl; C5-C 10 Cycloalkyl groups, preferably cyclohexyl; or linear or branched, saturated or unsaturated C1-C 30 Preferably, C1-C 10 An alkyl group, more preferably a C1-C5 alkyl group; preferably R is H-(CH2) n -COOR and, -(CH2) n COR, in the formula, R is the same or different, H;C5-C 10 Aryl group, preferably phenyl; C5-C 10 Cycloalkyl groups, preferably cyclohexyl groups; or linear or branched, saturated or unsaturated C1-C groups. 30 Preferably, C1-C 10 Alkyl, more preferably C1-C5 alkyl; preferably R is H-(CH2) n COR and, -(CH2) n CONR 4 R 5 And in the formula, R 4 and R 5 These are the same or different, H;C5-C 10 Aryl group (preferably a phenyl group); C5-C 10 Cycloalkyl group (preferably cyclohexyl); or C1-C 30 Preferably, C1-C 10 Alkyl, more preferably C1-C5 alkyl, linear or branched, saturated or unsaturated; preferably, R 4 and R 5 H is H - (CH2) n CONR 4 R 5 Selected from the group consisting of and Preferably, Z is (CH2) n -XR 2 R 3 , (CH2) n -COOR, (CH2)n CONR 4 R 5 And; However, at least one of the five-membered rings of the metallocene is substituted with a (CH2)n-PR2R3 group. R 1 They are identical or different, and formula CR 6 Selected from a group consisting of 3 groups, in the formula R 6 C1-C is linear or branched, saturated or unsaturated. 30 Alkyl, preferably C1-C 10 Alkyl, more preferably C1-C5 alkyl, and optionally containing at least one heteroatom, preferably O or N; the following formula R 7 -C(CH3)2 gem-dimethyl group, where R7 is C1-C 30 Alkyl, preferably C1-C 10 Alkyl, more preferably C1-C5 alkyl, linear or branched, saturated or unsaturated, and optionally containing at least one heteroatom, preferably O or N; M1 is selected from the group consisting of Fe, Ni, Co, Cr, V, Rh, Ru, Os, and Re, and is preferably Fe.

[0016] Preferably, the metallocene is selected from compounds having the following formula (I) or (II).

[0017] [ka]

[0018] In the formula, Z may be the same or different, (CH2) n -PR 2 R 3 It is represented as, n is either 0 or 1. R 2 and R 3 They may be the same or different, C5~C 10 An aryl group, preferably a phenyl group, C5-C 10A cycloalkyl group, preferably a cyclohexyl group, or C1-C 30 Preferably, C1~C 10 More preferably, linear or branched saturated or unsaturated alkyl groups of C1 to C5, preferably R 2 and R 3 These may be the same or different groups, and represent a phenyl group, a cyclohexyl group, an isopropyl group, a tert-butyl group, or a furyl group. R 1 These may be the same or different, and the following formula CR 6 Selected from the card group represented by 3, in the formula, R 6 is C1~C 30 Preferably, C1~C 10 More preferably, a linear or branched saturated or unsaturated alkyl group of C1 to C5, optionally containing at least one heteroatom, preferably O or N, or the following formula R 7 -C(CH3)2 is a gem-dimethyl group, where R is in the formula. 7 is C1~C 30 Preferably, C1~C 10 More preferably, a linear or branched saturated or unsaturated alkyl group of C1 to C5, optionally containing at least one heteroatom, preferably O or N.

[0019] In the above embodiment, R 1 It is preferably tert-butyl.

[0020] Conveniently, each five-membered ring of metallocene is defined by the formula (CH2) above. n -XR 2 R 3 The nanoparticles are substituted with at least one identical or different group represented by (where X is P), and are arranged in the form of a network of different nanoparticles linked by metallocene ligands.

[0021] The present invention - Use of the metal nanoparticles according to any one of claims 1 to 8 as a catalyst for the recovery of H2 by hydrolysis or solvation of an amine borane compound or a hydrazine borane compound, wherein the solvent is preferably a polar hydrogen donor, more preferably an alcohol, and even more preferably methanol or ethanol. -The present invention relates to a process for recovering H2 from an amine borane or hydrazine borane, comprising hydrolyzing or solvent-decomposing an amine borane compound in the presence of metal nanoparticles according to any one of claims 1 to 8.

[0022] Preferably, the amine borane is of the formula NR2'H-BH3 or BH3-NR2'-(CH2) m It is represented as -NR2'-BH3, where R' may be the same or different, and H, C5~C 10 The aryl group, preferably a phenyl group, or C1-C 30 Preferably, C1~C 10 Alkyl, more preferably C1-C5 linear or branched saturated or unsaturated alkyl group, where m is 1, 2, or 3, and preferably the amine borane is NH3-BH3(AB), NMeH2-BH3 (methylamine borane MeAB), NMe2H-BH3 (dimethylamine borane DMAB), or H3B-NH2CH2CH2H2N-BH3 (ethylenediamine bisborane EDAB).

[0023] In one embodiment, solubility is carried out using ethanol or methanol.

[0024] Preferably, hydrolysis or solvent decomposition is carried out in a temperature range of -90°C to 100°C, more preferably in a temperature range of -40°C to 80°C, even more preferably in a temperature range of 0°C to 30°C, and more preferably at 20°C.

[0025] In one embodiment, the method according to the present invention further includes a step of recycling nanoparticles, which is preferably carried out by recovering the nanoparticles and washing the recovered nanoparticles with a solvent used for hydrolysis or solvation of amine borane or hydrazine borane. [Brief explanation of the drawing]

[0026] Ditopic and polytopic metallocene ligands offer the advantage of a controlled structure, which not only stabilizes the surface of individual nanoparticles through strong bonding but also binds the nanoparticles together in a dense network. The formation of this network during nanoparticle growth allows for advantageous control of nanoparticle size, preferably in the range of 1–2 nm. Such small sizes have the advantage of leading to high activity due to a larger metal surface area. This approach, which stabilizes nanoparticles without external support such as oxides or carbon, also overcomes the potential instability of isolated nanoparticles. [Figure 1] This represents fragments of three nanoparticles stabilized with a ditopic metallocene ligand according to the present invention, forming a network. [Modes for carrying out the invention]

[0027] The present invention will be described in more detail, without being limited to the following description.

[0028] The following terms and expressions used in this specification are defined as follows:

[0029] When used herein, "C1~C n The term "alkyl" refers to a linear, branched, or cyclic alkyl group having 1 to n carbon atoms (C n H 2n+1This refers to ). Suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, pentyl and its isomers (e.g., n-pentyl, isopentyl), and hexyl and its isomers (e.g., n-hexyl, isohexyl).

[0030] All other terms used in this description of the present invention have meanings well known in the art.

[0031] The present invention relates to metal nanoparticles stabilized by metallocene ligands, wherein each five-membered ring of the metallocene ligand is -(CH2) n -XR 2 R 3 And in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, more preferably 0. X is a metallic coordination atom, preferably P, N, B, or Al, more preferably P, N, or B, even more preferably P or N, and even more preferably P. R 2 and R 3 They may be the same or different, C5~C 10 Aryl group, preferably phenyl group, C5-C 10 Cycloalkyl groups, preferably cyclohexyl groups, 1 or 2 heteroatoms, preferably 5-10 membered heteroaryl groups containing O or N, for example, linear or branched C1-C5 alkyl groups, for example, furyl groups, 1 or 2 heteroatoms, preferably 5-10 membered heterocycles containing O or N, or C1-C 30 Alkyl alkyl groups, preferably C1-C 10 The term represents an alkyl group, more preferably a linear or branched, saturated or unsaturated C1-C5 alkyl group, and preferably R 2 and R 3 R may be the same or different and represents a phenyl group, a cyclohexyl group, an isopropyl group, a tert-butyl group, or a furyl group, or R2 and R 3 Preferably, when X is P, together with X, a 5-10 membered heteroring can be formed which includes one heteroatom selected from O, N, and S, preferably N, and which may be substituted with a linear or branched C1-C5 alkyl group and / or N(linear or branched C1-C5 alkyl group)2 -(CH2) n -XR 2 R 3 and, -(CH2) n -COOR, in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, more preferably 0. R may be the same or different, H;C5~C 10 An aryl group, preferably a phenyl group; C5~C 10 A cycloalkyl group, preferably a cyclohexyl group; or C1-C 30 Preferably, C1~C 10 More preferably, it represents a linear or branched, saturated or unsaturated alkyl group of C1 to C5, and preferably R is H -(CH2) n -COOR and, -(CH2) n COR, in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, more preferably 0. R may be the same or different, H;C5~C 10 An aryl group, preferably a phenyl group; C5~C 10 A cycloalkyl group, preferably a cyclohexyl group; or C1-C 30 Preferably, C1~C 10 More preferably, a linear or branched, saturated or unsaturated alkyl group of C1-C5, and preferably, R is H -(CH2) n COR and, -(CH2) n CONR 4 R 5 And in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, more preferably 0. R 4 and R 5 These may be the same or different, H, C5~C 10 An aryl group, preferably a phenyl group, C5-C 10 A cycloalkyl group, preferably a cyclohexyl group, or C1-C 30 Preferably, C1~C 10 More preferably, it represents a linear or branched, saturated or unsaturated alkyl group of C1 to C5, or R 4 and R 5 It may form a 5-10 membered heterocycle with the N atom, preferably R 4 and R 5 H is H, However, at least one of the five-membered rings of the metallocene is at least one (CH2) n -PR 2 R 3 Provided that it is substituted with the base, Each 5-membered ring of metallocene may further optionally contain one or more, preferably one, identical or different R 1 It may be substituted with a base, and R1 is in the formula CR 6 The base represented by 3, in the formula, R 6 The carbon chain is linear or branched, saturated or unsaturated, preferably containing at least one heteroatom, more preferably O or N, and C1-C 30 Alkyl alkyl groups, preferably C1-C 10 A group selected from the group consisting of alkyl groups, more preferably C1-C5 alkyl groups, and formula R 7 A geminal dimethyl group represented by -C(CH3)2, where R 7 The carbon chain is linear or branched, saturated or unsaturated, preferably containing at least one heteroatom, more preferably O or N, and C1-C 30 Alkyl alkyl groups, preferably C1-C 10 A group selected from the group consisting of alkyl groups, more preferably C1-C5 alkyl groups, In the formula, the metal of the metallocene is selected from the group consisting of Fe, Ni, Co, Cr, V, Rh, Ru, Os, and Re, and is preferably Fe. The atomic ratio of the metal in the nanoparticles to the metal in the metallocene is 5 / 1 or greater, preferably in the range of 5 / 1 to 20 / 1, and more preferably in the range of 10 / 1 to 20 / 1, and is substituted by at least one identical or different group selected from this group.

[0032] Preferably, the metal nanoparticles have an average diameter consisting of 0.5 to 50 nm, more preferably 0.5 to 10 nm, and even more preferably 0.5 to 2 nm, as measured by transmission electron microscopy in the solid state or dynamic light scattering in a liquid dispersion.

[0033] Preferably, in the metallocene ligand of the present invention, each 5-membered ring of the metallocene is (CH2) as defined above. n -XR 2 R 3 , (CH2) n -COOR or (CH2) n CONR 4 R 5 Preferably, (CH2) n -PR 2 R 3 , (CH2) n -COOR or (CH2) n CONR 4 R 5 It is substituted by at least one identical or different group selected from the group consisting of the following.

[0034] Preferably, in the metallocene ligand of the present invention, each 5-membered ring of the metallocene is -(CH2) n -XR 2 R 3 And, During the ceremony, n is 0 or 1, preferably 0. X is P or N, preferably P. R 2 and R 3They may be the same or different, C5~C 10 Aryl group, preferably phenyl group, C5-C 10 Cycloalkyl groups, preferably cyclohexyl groups, or linear or branched saturated or unsaturated C1-C1 groups. 30 Alkyl alkyl groups, preferably C1-C 10 Alkyl, more preferably C1-C5 alkyl, and preferably R 2 and R 3 -(CH2) may be the same or different, representing a phenyl group or a cyclohexyl group. n -XR 2 R 3 and -(CH2) n -COOR, in the formula, n is 0 or 1, preferably 0. R may be the same or different, H;C5~C 10 An aryl group, preferably a phenyl group; C5~C 10 A cycloalkyl group, preferably a cyclohexyl group; or C1-C 30 Preferably, C1~C 10 More preferably, a linear or branched, saturated or unsaturated alkyl group of C1-C5, preferably R is H -(CH2) n -COOR and, -(CH2)nCONR4R5, in the formula, n is 0 or 1, preferably 0. R 4 and R 5 These may be the same or different, H, C5~C 10 An aryl group, preferably a phenyl group, C5-C 10 A cycloalkyl group, preferably a cyclohexyl group, or a linear or branched, saturated or unsaturated C1-C group. 30 Preferably, C1~C 10 , more preferably representing C1-C5 alkyl groups, preferably R 4 and R 5 H is H - (CH2) n -COOR and, However, at least one of the five-membered rings of the metallocene is at least one (CH2) n -PR 2 R 3 Provided that it is substituted with the base, Each 5-membered ring of metallocene is in the formula CR 6 Selected from the 3 groups, identical or different R 1 It is substituted by the R group, 6 C1~C 30 Alkyl alkyl groups, preferably C1-C 10 Alkyl alkyl groups, more preferably linear or branched, saturated or unsaturated C1-C5 alkyl groups, and optionally containing at least one heteroatom, preferably O or N; the following formula R 7 -C(CH3)2 is a geminal dimethyl group, and R 7 C1~C 30 Alkyl alkyl groups, preferably C1-C 10 An alkyl group, more preferably a linear or branched, saturated or unsaturated alkyl group of C1 to C5, and optionally containing at least one heteroatom, preferably O or N. The metallocene is selected from the group consisting of Fe, Ni, Co, Cr, V, Rh, Ru, Os, and Re, and is preferably Fe.

[0035] In one embodiment, the metallocene ligand of the present invention is preferably selected from compounds of formula (I), (II), or (III), [ka] During the ceremony, n is 0, 1, 2, 3, or 4, preferably 0 or 1, more preferably 0. Z is -(CH2) n -XR 2 R 3 And in the formula, X is P, N, B, or Al, preferably P or N, more preferably P. R 2 and R3 These are the same or different, C5~C 10 Aryl group, preferably phenyl group; C5~C 10 Cycloalkyl groups, preferably cyclohexyl groups; 1 or 2 heteroatoms, preferably 5-10 membered heteroaryl groups containing O or N, which may be substituted with linear or branched C1-C5 alkyl groups, e.g., furyl groups; 1 or 2 heteroatoms, preferably 5-10 membered heterocyclic groups containing O or N; or C1-C 30 Preferably, it represents a linear or branched, saturated or unsaturated alkyl group of C1 to C10, more preferably C1 to C5, and preferably R 2 and R 3 R represents, either identically or differently, a phenyl group, a cyclohexyl group, an isopropyl group, a tert-butyl group, or a furyl group. 2 and R 3 X, preferably together with P when X is P, can form a 5-10 membered heterocycle (CH2) which includes one heteroatom selected from O, N, and S, preferably N, and may be substituted with a C1-C5 linear or branched alkyl group and / or N(C1-C5 linear or branched alkyl group)2. n -XR 2 R 3 and, -(CH2) n -COOR, in the formula, R may be the same or different, H;C5~C 10 An aryl group, preferably a phenyl group; C5~C 10 A cycloalkyl group, preferably a cyclohexyl group; or C1-C 30 Preferably, C1~C 10 , more preferably, C1~C 5 A linear or branched saturated or unsaturated alkyl group; preferably, R is H -(CH2) n -COOR and, -(CH2) n COR, in the formula, R may be the same or different, H;C5~C 10An aryl group, preferably a phenyl group; C5~C 10 A cycloalkyl group, preferably a cyclohexyl group; or a linear or branched saturated or unsaturated C1-C group. 30 Preferably, C1~C 10 , more preferably a C1-C5 alkyl group; preferably, R is H -(CH2) n COR and, -(CH2) n CONR 4 R 5 And in the formula, R 4 and R 5 They may be the same or different, H;C5~C 10 An aryl group, preferably a phenyl group; C5~C 10 A cycloalkyl group, preferably a cyclohexyl group; or C1-C 30 Preferably C1~C 10 More preferably, it represents a linear or branched, saturated or unsaturated alkyl group of C1 to C5, preferably R 4 and R 5 H is H - (CH2) n CONR 4 R 5 Selected from the group consisting of and However, in the metallocene represented by formula (I), at least one of the five-membered rings of the metallocene is (CH2) n -PR 2 R 3 Provided that it is substituted by the element, R 1 These may be the same or different, and the formula CR 6 A group represented by 3, where R 6 C1~C 30 an alkyl group, preferably C1-C 10 The alkyl group, more preferably a C1-C5 alkyl group, is linear or branched, saturated or unsaturated, and optionally contains at least one heteroatom, preferably O or N, and is of the following formula R 7 -C type CR 6The group represented by 3 (CH3) and the gem-dimethyl group represented by 2 are of the formula CR 6 Selected from the group consisting of groups represented by 3, R 7 These are linear or branched, saturated or unsaturated C1-C123 30 It is an alkyl group, preferably C1-C 10 An alkyl group, more preferably a C1-C5 alkyl group, which may optionally contain at least one heteroatom, preferably O or N, and preferably R 1 is, formula CR 6 It is a group represented by 3, in the formula R 6 These are linear or branched, saturated or unsaturated C1-C123 30 It is an alkyl group, preferably C1-C 10 Alkyl alkyl groups, more preferably C1-C5 alkyl groups -(CH2) n CONR 4 R 5 and, M1 is selected from the group consisting of Fe, Ni, Co, Cr, V, Rh, Ru, Os, and Re, and is preferably Fe.

[0036] Preferably, when the metallocene is represented by the above formula (I): n is 0 or 1, preferably 0; Z is -(CH2) n -XR 2 R 3 And in the formula, X is P, N, B, or Al, preferably P or N, preferably P; R 2 and R 3 They may be the same or different, C5~C 10 Aryl group, preferably phenyl group; C5~C 10 Cycloalkyl groups, preferably cyclohexyl groups; 1 or 2 heteroatoms, preferably 5-10 membered heteroaryl groups containing O or N, e.g., furyl groups; 1 or 2 heteroatoms, preferably 5-10 membered heterocyclic groups containing O or N; or linear or branched, saturated or unsaturated C1-C 30Preferably, C1-C 10 , more preferably, represents a C1-C5 alkyl group; preferably, R 2 and R 3 These may be the same or different groups, and may be a phenyl group, a cyclohexyl group, an isopropyl group, a tert-butyl group, or a furyl group, preferably a phenyl group or a cyclohexyl group represented by -(CH2) n -XR 2 R 3 and, -(CH2) n -COOR, in the formula, R may be the same or different, H;C5~C 10 Aryl group, preferably phenyl group; C5~C 10 Cycloalkyl groups, preferably cyclohexyl groups; or C1-C 30 Preferably, a linear or branched chain, saturated or unsaturated C1-C 10 , more preferably, represents a C1-C5 alkyl group; preferably, R is H -(CH2) n -COOR and, -(CH2) n CONR 4 R 5 And in the formula, R 4 and R 5 They may be the same or different, H;C5~C 10 Aryl group, preferably phenyl group; C5~C 10 Cycloalkyl groups, preferably cyclohexyl groups; or C1-C 30 Preferably, C1~C 10 More preferably, it represents a linear or branched C1-C5 saturated or unsaturated alkyl group; preferably R 4 and R 5 H is H - (CH2) n CONR 4 R 5 A selection is made from the group consisting of and . However, in the metallocene of formula (I), at least one of the five-membered rings of the metallocene is (CH2) n -PR 2 R 3The condition is that it is substituted with the base.

[0037] Preferably, when the metallocene is represented by the above formula (I): n is 0 or 1, preferably 0; Z is -(CH2) n -XR 2 R 3 And in the formula, X is P; R 2 and R 3 They may be the same or different, C5~C 10 Aryl group, preferably phenyl group, C5-C 10 Cycloalkyl groups, preferably cyclohexyl groups, 1 or 2 heteroatoms, preferably 5-10 membered heteroaryl groups containing O or N, such as furyl groups, 1 or 2 heteroatoms, preferably 5-10 membered heterocyclic groups containing O or N, or linear or branched, saturated or unsaturated C1-C 30 Alkyl alkyl groups, preferably C1-C 10 The alkyl group preferably represents a C1-C5 alkyl group, and preferably R 2 and R 3 -(CH2) may be the same or different and represent a phenyl group, a cyclohexyl group, an isopropyl group, a tert-butyl group, or a furyl group, more preferably a phenyl group or a cyclohexyl group. n -XR 2 R 3 and, -(CH2) n -COOR, in the formula, R may be the same or different, H;C5~C 10 Aryl group, preferably phenyl group; C5~C 10 Cycloalkyl groups, preferably cyclohexyl groups; or linear or branched, saturated or unsaturated C1-C1 groups. 30 Alkyl alkyl groups, preferably C1-C 10 An alkyl group, more preferably a C1-C5 alkyl group; preferably R is H, a -(CH2)n-COOR, -(CH2) n CONR 4 R 5 And in the formula, R 4 and R 5 They may be the same or different, H;C5~C 10 Aryl group, preferably phenyl group; C5~C 10 Cycloalkyl groups, preferably cyclohexyl groups; or linear or branched, saturated or unsaturated C1-C1 groups. 30 Alkyl alkyl groups, preferably C1-C 10 Alkyl, more preferably, represents a C1-C5 alkyl group; preferably, R 4 and R 5 It is selected from the group consisting of H -(CH2)nCONR4R5 and: However, in the metallocene represented by formula (I), at least one of the five-membered rings of the metallocene is (CH2) n -PR 2 R 3 The condition is that it is substituted with the base.

[0038] Preferably, the metallocene ligand of the present invention is represented by formula (I) or (II), and more preferably by formula (I).

[0039] In the above definitions of each metallocene ligand, preferably, (CH2) n -XR 2 R 3 In: n is 0; X is P; R 2 and R 3 They may be the same or different, C5~C 10 An aryl group, preferably a phenyl group, C5-C 10 A cycloalkyl group, preferably a cyclohexyl group, preferably R 2 and R 3 These may be the same or different, and represent a phenyl group or a cyclohexyl group.

[0040] In the above definitions of metallocene ligands, preferably, (CH2) n -COOR, n is 0; R is H.

[0041] In the above definitions of metallocene ligands, preferably, (CH2) n CONR 4 R 5 In, n is 0; R 4 and R 5 H is H.

[0042] In the above definitions of metallocene ligands, Preferably, (CH2) n -XR 2 R 3 in the case of: n is 0; X is P; R 2 and R 3 These are the same or different, C5~C 10 Aryl group, preferably phenyl; C5~C 10 Represents a cycloalkyl group, preferably a cyclohexyl group; preferably, R 2 and R 3 These represent phenyl or cyclohexyl, either identical or distinct; Preferably, (CH2) n -For COOR: n is 0; R is H; and Preferably, (CH2) n CONR 4 R 5 in the case of: n is 0; R 4 and R 5 H is H.

[0043] Preferably, in the metallocene according to the present invention, and preferably in the metallocene of formula (I), (II), or (III), R1 It is tert-butyl.

[0044] In each embodiment illustrating the metallocene ligand according to the present invention, the metal of the metallocene is preferably iron.

[0045] Preferably, the metallocene of the present invention is selected from the following:

[0046] [ka]

[0047] The metallocene ligands according to the present invention are based on methods known to those skilled in the art, particularly those described in *Conformational Control of Metallocene Backbone by Cyclopentadienyl Ring Substitution: A New Concept in Polyphosphane Ligands Evidenced by “Through-Space” Nuclear Spin-Spin Coupling. Application in Heteroaromatics Arylation by Direct CH Activation. Organometallics 2009, 28, 3152-3160; FR 3014871 (Non-Patent Literature 1)* and *Highly Functionalized Ferrocenes. Lerayer, E.; Radal, L.; Nguyen, T.-A.; Dwadnia, N.; Cattey, H.*. It can be synthesized according to the process disclosed in Amardeil, R.; Pirio, N.; Roger, J.; Hierso, J.-C. European Journal of Inorganic Chemistry (2020), 419-445 (Non-Patent Literature 2).

[0048] Each five-membered ring of metallocene is defined by formula (CH2) above. n -XR 2 R 3 If X is P, and is substituted by at least one identical or different group, the nanoparticles are arranged in the form of a network of different nanoparticles bonded by metallocene ligands.

[0049] Advantageously, when a nanoparticle network is formed, the average diameter of each nanoparticle, as measured by transmission electron microscopy in the solid state or by diffuse light scattering in a liquid dispersion, is 0.5 to 10 nm, preferably 0.5 to 2.5 nm, and more preferably 0.5 to 2 nm. Advantageously, the inventors have found that the size of the nanoparticles can be controlled to a minimum size by network formation.

[0050] The metal of the nanoparticles is preferably ruthenium, nickel, platinum, rhodium, or cobalt, preferably nickel or ruthenium, and more preferably ruthenium. This preferred embodiment can be combined with any of the above definitions of metallocene ligands and preferred metallocene ligands.

[0051] Nanoparticles stabilized by the metallocene ligand according to the present invention can be produced by mixing an excess amount of a metal-organic complex as a molecular precursor for nanoparticle formation with a ditopic or polytopic metallocene ligand in a suitable solvent (preferably toluene, THF, etc. that do not coordinate or coordinate weakly) in the presence of a metal reducing agent (preferably hydrogen H2, LiAlH4, NaBH4, etc.) at a mild temperature (less than 100°C) and for a short reaction time (preferably less than 24 hours).

[0052] Preferably, due to its two donor sites and its rotational flexibility, the ditopic metallocene ligand can coordinate a metal atom as a chelating agent on the surface of a single nanoparticle or as a linker between the surfaces of two nanoparticles.

[0053] The atomic ratio of the metal in the nanoparticles to the metal in the metallocene is greater than 5 / 1, preferably 5 / 1 to 20 / 1, and more preferably 10 / 1 to 20 / 1.

[0054] A typical example of a metal-organic complex as a molecular precursor for nanoparticle formation is the bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) complex. The solvent is preferably the aprotic solvent tetrahydrofuran (THF). The ditopic metallocene ligand is preferably racemic 1,1'-bis(diphenylphosphino)-3,3'-di-tert-butylferrocene (L2). The resulting solution is preferably pressurized with 3 bar of H2 and heated at 60°C for 16 hours with stirring. Nanoparticles stabilized by the metallocene ligand according to the present invention are distinguished as metal complexes formed from the reaction of one metal and one ligand, or when a ratio of less than 5 metals to one ligand is used in the synthesis.

[0055] The present invention also relates to using nanoparticles stabilized by the metallocene ligands defined above as catalysts for hydrogen supply by hydrolysis or solvent decomposition of amine borane compounds and hydrazine borane compounds. Preferably, the present invention relates to using nanoparticles stabilized by the metallocene ligands as catalysts for hydrogen recovery by hydrolysis or solvent decomposition of ammonia borane.

[0056] The present invention also relates to a process for supplying H2 from an amine borane or hydrazine borane compound, comprising hydrolyzing or solvating the amine borane or hydrazine borane compound in the presence of the nanoparticles defined above. Preferably, the present invention also relates to a process for supplying H2 from an amine borane or hydrazine borane compound, comprising hydrolyzing or solvating the amine borane or hydrazine borane compound in the presence of the nanoparticles defined above.

[0057] Advantageously, the supply of H2 in this invention can be carried out by hydrolysis or solvation of an amine borane or hydrazine borane compound. Using water or a solvent allows the process to be carried out over a wide temperature range. In fact, when using water, the process can be carried out between 0°C and 100°C, but by selecting a different solvent, it is possible to carry out the process at lower temperatures. This is particularly important in applications where external temperature is a factor, such as in the automotive sector.

[0058] Therefore, this process can be carried out at temperatures of -90°C to 100°C, preferably -40°C to 80°C, more preferably 0°C to 30°C, and even more preferably 20°C.

[0059] Preferably, the solvent is a polar hydrogen donor. The polar hydrogen donor is preferably an alcohol. The alcohol is, for example, a monoalcohol or a polyol, and is preferably a monoalcohol. The monoalcohol can be selected from ethanol or methanol. As the polyol, for example, polyalkylene glycol, preferably polyethylene glycol, is used. As the solvent, methanol or ethanol is preferably used.

[0060] The amine boranes that can be used in the present invention are not particularly limited. Preferably, the amine is of the formula NR2'H→BH3 or BH3←NR2'-(CH2) m -NR2'→BBH3 is represented by the formula where R' is the same or different H, linear or branched, saturated or unsaturated C5-C 10 An aryl group, preferably phenyl, or C1-C 30 Preferably, C1-C 10Alkyl, more preferably C1-C5 alkyl, where m is 1, 2, or 3. Preferably, the amine borane is NH3 → BH3 (ammonia borane, AB), NMeH2 → BH3 (methylamine borane, MeAB), NMe2H → BH3 (dimethylamine borane, DMAB), or H3B ← NH2(CH2)2H2N → BH3 (ethylenediamine bisborane, EDAB). The hydrazine borane according to the present invention is a compound of the formula N2H4-BH3(HB).

[0061] Preferably, in the H2 delivery process from amine borane or hydrazine borane according to the present invention, the nanoparticles according to the present invention are used such that the molar ratio of metal to amine borane from the nanoparticles is 0.0001 to 1, preferably 0.01 to 0.02.

[0062] Advantageously, the nanoparticles according to the present invention can be recycled and reused in the process. Recycling of the nanoparticles according to the present invention can be carried out by recovering the nanoparticles and then washing the recovered nanoparticles with the solvent used for hydrolysis or solvation of the amine borane or hydrazine borane, optionally in combination with or in combination with a nonpolar hydrocarbon solvent (preferably pentane). Recovery of the nanoparticles according to the present invention can be carried out by any method known to those skilled in the art, for example, by centrifugation.

[0063] (Examples) The present invention will be described below based on the following non-limiting embodiments.

[0064] Materials and methods: (General synthesis conditions) All reactions were carried out in Schlenk tubes, Fischer-Porter vials, or two-necked flasks under a dry argon atmosphere. All reagents and precursors were purchased from commercial suppliers and used without purification. The bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) complex was purchased commercially. All ligands were modified according to processes described in scientific literature, and in particular, Smaliy, RV, Beauperin, M., Cattey, H., Meunier, P., Hierso, J.-C., Roger, J., Doucet, H., Coppel, Y. "Conformational control of metallocene skeletons by cyclopentadienyl ring substitution: A novel concept of polyphosphane ligands demonstrated by trans-spatial nuclear spin-spin coupling. Application to heteroaromatic arylation by direct CH activation." Organometallics 2009, 28, 3152-3160; FR 3014871; (Non-patent Literature 3), and Highly Functionalized Ferrocenes. Lerayer, E.; Radal, L.; Nguyen, T.-A.; Dwadnia, N.; Cattey, H.; Amardeil, R.; Pirio, N.; Roger, J.; Hierso, J.-C. European The synthesis was performed by referring to Journal of Inorganic Chemistry (2020), 419-445 (Non-Patent Literature 4).

[0065] (Synthesis of ligands L1 to L6) (Preparation of L1) [ka]

[0066] (Preparation of L2 and L3) [ka]

[0067] (Preparation of L4) [ka]

[0068] (Preparation of L5) [ka]

[0069] (Preparation of L6) [ka]

[0070] (General procedure for the synthesis of Ru nanoparticles stabilized by ferrocenylpolyphosphine and monophosphine hybrid ligands L1-L6) 0.79 mmol of bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) complex and the desired ligands (L1-L6) were placed in a Fischer-Porter vial and left under vacuum for 30 minutes. Next, 80 mL of anhydrous tetrahydrofuran (THF) was added, and the mixture was stirred under argon at 20°C for 1 hour. The resulting clear solution was pressurized with 3 bar of H2. The solution was heated overnight at 60°C with stirring. After this period, excess H2 was removed, and the volume of the solvent was reduced to approximately 10 mL under vacuum. Next, 40 mL of pentane was added to the colloidal suspension. After 2 hours, the black precipitate was washed with pentane, and after centrifugation, the solvent was removed to obtain dark powdery particles.

[0071] (General procedure for synthesizing L2-stabilized Ni nanoparticles) Anhydrous toluene was added to a Schlenk tube and degassed by a freeze-pump-thaw cycle. Next, the degassed anhydrous toluene was placed in a glove box. In the glove box, the bis(1,5-cyclooctadiene)nickel(0)(Ni(COD)2) complex (0.727 mmol) and ligand L2 were introduced into a Fischer-Porter vial. Next, 24 mL of degassed anhydrous toluene (0.03 MNi(COD)2) was added to the Fischer-Porter vial. The Fischer-Porter vial was removed from the glove box, and the mixture was stirred under an argon atmosphere at 20°C for 30 minutes to 1 hour. The resulting clear solution was pressurized with 3 bar of H2. The solution was heated overnight at 80°C with stirring. After this period, excess H2 was removed, and the volume of the solvent was reduced to approximately 10 mL under vacuum. Next, 20 mL of pentane, degassed by a freeze-pump-thaw cycle, was added to the colloidal suspension. After 2 hours, the black precipitate was washed three times with pentane, degassed using a freeze-pump-thaw cycle (including an accelerated step, at 25°C, 7500 rpm, 10 minutes), and centrifuged. After three centrifugations, the solvent was removed under vacuum, yielding nanoparticles as a dark-colored powder.

[0072] (General procedure for dehydrogenation of amine borane (AB) by catalytic recycling) In a 25 mL two-necked round-bottom flask, a colloidal suspension of R nanoparticles (0.02 mmol Ru) in a 2 mL solvent (temperature-controlled to 25°C) was added using a syringe while stirring at 600 rpm. A solvent solution of ammonia borane (AB, NH3BH3) (4 mL, 1 mmol AB) was added. H2 production was monitored by recording the increase in pressure in a gas burette. In AB dehydrogenation experiments using catalyst recycling, the catalyst was recovered by centrifugation and washed three times with pentane for use in the next cycle. The solvent (2 mL) and the solvent solution of AB (4 mL, 1 mmol) were sequentially added to the nanoparticles, and the amount of H2 produced was monitored again. This process was repeated five or more times.

[0073] (General procedure for dehydrogenation of amine borane (AB) using Ni-based nanoparticles) In a 25 mL two-neck round-bottom flask, while stirring at 600 rpm, a solution of ammonia borane (AB, NH₃BH₃) in a solvent (3 mL, 1 mmol AB) was added to a colloidal suspension of Ni nanoparticles (0.02 mmol Ni) in a solvent (3 mL) thermostatically adjusted to 25 °C using a syringe. The generation of H₂ was monitored by recording the increase in pressure in a gas burette.

[0074] (Preparation of non-stabilized particles (comparative example) The bis(2-methylallyl)(1,5-cyclooctadiene)ruthenium(II) complex was pressurized with 3 bar of H₂ at 60 °C in THF for 18 hours. After evaporating the THF, the particles were precipitated with pentane and recovered by centrifugation.

[0075] The bis(1,5-cyclooctadiene)nickel(0) complex was pressurized with 3 bar of hydrogen in toluene at 80 °C overnight. After evaporating the toluene, the particles were precipitated with pentane and recovered by centrifugation.

[0076] The average particle size was measured by transmission electron microscopy in the solid state or by diffusing light scattering in a liquid dispersion and is as follows. Ru / L1(20 / 1): 2.6 nm Ru / L1(10 / 1): 2.2 nm Ru / L1(5 / 1): 2.1 nm Ru / L1(1 / 1): 1 nm Ru / L2(10 / 1): 2.5 nm Ru / L3(20 / 1): 1.8 nm Ru / L3(10 / 1): 1.9 nm Ru / L3(5 / 1): 1.8 nm Ru / L4(10 / 1): 2.3 nm Ru: 3 nm

[0077] (Results of hydrolysis of ammonia borane) The conditions for the hydrolysis of ammonia borane at 298 K (25 °C) are as follows: AB: 187 mM, H₂O 6 mL, Ru: 0.02 mmol, 3.33 mM Ni: 0.02 mmol TOF(mol H2 .mol cat -1 .min -1 ) is calculated as follows: mmolH2 / (mmolRu(or Ni).min -1 ).

[0078] [Table 1]

[0079] The yield of the reaction using unstabilized Ni particles was 10%, while the yield of the reaction in assay 45 was 58%, and the yield of the reaction in assay 43 was 73%.

[0080] (Results of hydrolysis of ammonia borane (AB) at different concentrations)

[0081] [Table 2]

[0082] (Results of solvent decomposition of ammonia borane and ethanol) [Table 3]

[0083] (Results of solvent decomposition of ammonia borane and methanol) [Table 4]

[0084] The results clearly show that the nanoparticles of the present invention can deliver large amounts of H2 in a short time using water or alcohol as a solvent, compared to the prior art complexes (assays 4, 8, 12, 16, and 20, comparison Cx) and also compared to particles not stabilized by ditopic and polytopic metallocene ligands L1-L6 (comparisons 1, 2, 3, and 4). This is partly due to the organization of the network that controls the small size of the nanoparticles and promotes overall stability. In this process, various solvents such as water and alcohol can be used, so it can be carried out regardless of temperature, that is, even at temperatures far below 0 °C. When the activity measured by TOF (min -1 ) is higher, it increases significantly compared to the current value.

[0085] (Results of hydrolysis or solvolysis of AB with the nanocatalyst reused over 5 cycles) (Results of hydrolysis of non-stabilized particles)

[0086]

Table 5

[0087] (Results of Ru / L1 (20 / 1))

Table 6

[0088] (Results of Ru / L2 (20 / 1))

Table 7

[0089] (Results of Ru / L3 (20 / 1))

Table 8

[0090] (Results of Ru / L4 (20 / 1))

Table 9

[0091] (Ru / L5 results (20 / 1)) [Table 10]

[0092] (Ru / L6 results (20 / 1)) [Table 11]

[0093] These results demonstrate that the nanocatalyst system of the present invention is reusable within the process.

Claims

1. Metal nanoparticles stabilized by a metallocene ligand, Each five-membered ring of metallocene is - (CH ２ ) n-XR ２ R ３ And in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, preferably 0. X is a metal coordination atom, preferably P, N, B, or Al, preferably P, N, or B, preferably P or N, preferably P. R ２ and R ３ may be the same or different and are C ５ -C １０ aryl groups, preferably phenyl; C ５ -C １０ cycloalkyl groups, N, preferably cyclohexyl; 5- to 10-membered heteroaryl containing one or two heteroatoms, preferably O or N, and optionally substituted, for example, by a linear or branched C1-C5 alkyl group, for example, a furyl group; a 5- to 10-membered heterocyclic ring containing one or two heteroatoms, preferably O or N; or C １ -C ３０ , preferably linear or branched, saturated or unsaturated C １ -C １０ alkyl, more preferably C １ -C ５ alkyl group; preferably, R ２ and R ３ may be the same or different and represent phenyl, cyclohexyl, isopropyl, tert-butyl or furyl; or R ２ and R ３ together with X, preferably when X is P, may contain one heteroatom selected from O, N, S, preferably N, and optionally, for example, a linear or branched C １ -C ５ alkyl group and / or N(linear or branched C １ -C ５ alkyl group) ２ and form a 5- to 10-membered ring heterocycle optionally substituted by -(CH ２ )n-XR ２ R ３ and - (CH ２ ) ｎ -COOR, in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, preferably 0. R may be the same or different, H;C ５ ~C １０ Aryl group, preferably phenyl group; C ５ ~C １０ Cycloalkyl groups, preferably cyclohexyl groups; or linear or branched, saturated or unsaturated C １ ~C ３０ Preferably, C １ -C １０ Alkyl, more preferably C １ -C ５ Alkyl alkyl group; preferably, R is H - (CH ２ ) ｎ -COOR and, - (CH ２ ) ｎ COR, in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, preferably 0; R may be the same or different, H;C ５ ~C １０ Aryl group, preferably phenyl group; C ５ ~C １０ Cycloalkyl groups, preferably cyclohexyl groups; or linear or branched, saturated or unsaturated C １ ~C ３０ Preferably, C １ ~C １０ Alkyl, more preferably C １ -C ５ Alkyl alkyl group; preferably, R is H - (CH ２ ) ｎ COR and, - (CH ２ ) ｎ CONR ４ R ５ And in the formula, n is 0, 1, 2, 3, or 4, preferably 0 or 1, preferably 0. R ４ and R ５ H and C may be the same or different. ５ ~C １０ Aryl group, preferably phenyl group; C ５ ~C １０ Cycloalkyl groups, preferably cyclohexyl groups, or linear or branched, saturated or unsaturated C １ ~C ３０ Preferably, C １ ~C １０ Alkyl, more preferably C １ ~C ５ Alkyl, or R ４ and R ５ It can combine with N atoms to form a 5- to 10-membered heterocycle, preferably R ４ and R ５ is H - (CH ２ ) ｎ CONR ４ R ５ Substituted by at least one identical or different group selected from the group consisting of and , However, at least one of the five-membered rings of metallocene must be at least one (CH ２ ) ｎ - PR ２ R ３ It is substituted by the group, Each 5-membered ring of the metallocene is substituted with one or more, preferably one, R selected from the group consisting of radicals of the formula CR ６ ３ (identical or different), and in the formula, R １ may be a linear or branched, saturated or unsaturated C ６ to C １ alkyl, preferably C ３０ to C １ alkyl, more preferably C １０ to C １ alkyl group, and optionally contains at least one heteroatom, preferably O or N; the gem-dimethyl group of the following formula R ５ -C(CH ７ ) ３ ２ where in the formula, R ７ is a linear or branched, saturated or unsaturated C １ to C ３０ alkyl, preferably C １ to C １０ alkyl, more preferably C １ to C ５ alkyl group, and optionally contains at least one heteroatom, preferably O or N; The metal of the metallocene is selected from the group consisting of Fe, Ni, Co, Cr, V, Rh, Ru, Os, and Re, preferably Fe; the atomic ratio of the nanoparticle metal to the metal of the metallocene is 5 / 1 or more, preferably 5 / 1 to 20 / 1, and preferably 10 / 1 to 20 / 1, in the metal nanoparticle.

2. A metal nanoparticle according to claim 1, wherein the metal of the nanoparticle is ruthenium, nickel, platinum, rhodium, or cobalt, preferably ruthenium or nickel, and more preferably ruthenium.

3. A metal nanoparticle according to claim 1 or 2, - (CH ２ ) ｎ -XR ２ R ３ In: n is 0 or 1, preferably 0; X is P or N, preferably P; R ２ and R ３ C may be the same or different. ５ ~C １０ An aryl group, preferably a phenyl group; C ５ ~C １０ Cycloalkyl groups, preferably cyclohexyl groups; or linear or branched, saturated or unsaturated C １ ~C ３０ Preferably, C １ ~C １０ Alkyl, more preferably C １ ~C ５ It is an alkyl group; preferably, R ２ and R ３ These represent phenyl or cyclohexyl, either identical or distinct; - (CH ２ ) ｎ - In COOR: n is 0 or 1, preferably 0; R may be the same or different, H;C ５ ~C １０ An aryl group, preferably a phenyl group; C ５ ~C １０ Cycloalkyl groups, preferably cyclohexyl groups; or linear or branched, saturated or unsaturated C １ ~C ３０ Preferably, C １ ~C １０ Alkyl, more preferably C １ ~C ５ Alkyl alkyl groups, preferably where R is H, - (CH ２ ) ｎ CONR ４ R ５ In: n is 0 or 1, preferably 0. R ４ and R ５ H and C may be the same or different. ５ ~C １０ An aryl group, preferably a phenyl group, and C ５ -C １０ Cycloalkyl groups, preferably cyclohexyl groups, or linear or branched, saturated or unsaturated C １ ~C ３０ Preferably, C １ ~C １０ Alkyl, more preferably C １ ~C ５ Alkyl alkyl group, preferably R ４ and R ５ H is a metal nanoparticle.

4. Metal nanoparticles according to any one of claims 1 to 3, wherein the metal of the metallocene is iron.

5. A metal nanoparticle according to any one of claims 1 to 4, wherein the metallocene is selected from compounds having the following formulas (I), (II), or (III): 【Chemistry 1】 During the ceremony: n is either 0 or 1, Z is: -(CH ２ ) n -XR ２ R ３ And in the formula, R ２ and R ３ C may be the same or different. ５ ~C １０ Aryl group, preferably phenyl; C ５ ~C １０ A cycloalkyl group, preferably a cyclohexyl group; one or two heteroatoms, preferably containing O or N, and optionally, for example, linear or branched C. １ -C5 alkyl groups, e.g., 5-10 membered heteroaryls substituted with furyl; 5-10 membered heterocycles containing 1 or 2 heteroatoms, preferably O or N; or linear or branched, saturated or unsaturated C １ ~C ３０ Preferably, C １ ~C １０ Alkyl alkyl group, more preferably C １ ~C ５ Alkyl alkyl group, preferably R ２ and R ３ R may be the same or different, and represents phenyl, cyclohexyl, isopropyl, tert-butyl, or furyl, or ２ and R ３ It preferably includes, along with X, one heteroatom selected from O, N, and S, preferably N, and optionally, for example, linear or branched C, if X is P, and if X is P. １ ~C ５ Alkyl alkyl groups and / or N (linear or branched C) １ ~C ５ (Alkyl group) 2 It can form a 5- to 10-membered heterocycle which may be substituted with -(CH ２ ) n -XR ２ R ３ and, - (CH ２ ) ｎ -COOR, in the formula R may be the same or different, H;C ５ ~C １０ Aryl group, preferably phenyl; C ５ ~C １０ Cycloalkyl groups, preferably cyclohexyl; or linear or branched, saturated or unsaturated C １ ~C ３０ Preferably, C １ ~C １０ Alkyl alkyl group, more preferably C １ -C ５ It is an alkyl group; preferably R is H - (CH ２ ) ｎ -COOR and, - (CH ２ ) ｎ COR, in the formula, R may be the same or different, H;C ５ ~C １０ Aryl group, preferably phenyl; C ５ ~C １０ Cycloalkyl groups, preferably cyclohexyl groups; or linear or branched, saturated or unsaturated C groups. １ -C ３０ Preferably, C １ -C １０ Alkyl, more preferably C １ -C ５ Alkyl alkyl group; preferably, R is H - (CH ２ ) ｎ COR and, - (CH ２ ) ｎ CONR ４ R ５ And in the formula, R ４ and R ５ H;C may be the same or different. ５ ~C １０ Aryl group, preferably phenyl group; C ５ ~C １０ Cycloalkyl groups, preferably cyclohexyl groups; or linear or branched, saturated or unsaturated C groups. １ ~C ３０ Preferably, C １ -C １０ Alkyl, more preferably C １ -C ５ Alkyl alkyl group; preferably, R ４ and R ５ is H - (CH ２ ) ｎ CONR ４ R ５ And, selected from, Preferably, Z is (CH ２ ) ｎ -XR ２ R ３ , (CH ２ ) ｎ - COOR, (CH ２ ) ｎ CONR ４ R ５ And, However, at least one of the five-membered rings of metallocene is (CH ２ ) ｎ - PR ２ R ３ It is substituted with the base, R １ These may be the same or different, and formula CR ６ ３ Selected from the group consisting of the elements, where R ６ C １ ~C ３０ Alkyl, preferably linear or branched, saturated or unsaturated C １ ~C １０ Alkyl, more preferably C １ ~C ５ It is an alkyl group, and optionally contains at least one heteroatom, preferably O or N; the following formula R ７ -C(CH ３ ) ２ The gem-dimethyl group is a linear or branched, saturated or unsaturated C. １ ~C ３０ Alkyl, preferably C １ ~C １０ Alkyl, more preferably C １ -C ５ It is an alkyl group, and optionally comprises at least one heteroatom, preferably O or N; M １ The nanoparticles are selected from the group consisting of Fe, Ni, Co, Cr, V, Rh, Ru, Os, and Re, and are preferably Fe.

6. A metal nanoparticle according to any one of claims 1 to 5, wherein the metallocene is selected from compounds having the following formula (I) or (II): 【Chemistry 2】 In the formula, Z may be the same or different, (CH ２ ) ｎ - PR ２ R ３ It is represented as, n is either 0 or 1, R ２ and R ３ They may be the same or different, C ５ ~C １０ An aryl group, preferably a phenyl group, C ５ ~C １０ A cycloalkyl group, preferably a cyclohexyl group, or C １ ~C ３０ Preferably, C １ ~C １０ , more preferably, C １ ~C ５ A linear or branched saturated or unsaturated alkyl group, preferably R ２ and R ３ These may be the same or different groups, and represent a phenyl group, a cyclohexyl group, an isopropyl group, a tert-butyl group, or a furyl group. R １ These may be the same or different, and the following formula CR ６ ３ Selected from the base group represented by the formula, where R ６ C is a linear or branched saturated or unsaturated C １ ~C ３０ Preferably, C １ ~C １０ , more preferably, C １ ~C ５ The alkyl group is, optionally containing at least one heteroatom, preferably O or N, or the following formula R ７ -C(CH ３ ) ２ This is a gem-dimethyl group represented by the formula, where R ７ is C １ ~C ３０ Preferably, C １ ~C １０ , more preferably, C １ ~C ５ Metal nanoparticles comprising linear or branched saturated or unsaturated alkyl groups, optionally containing at least one heteroatom, preferably O or N.

7. Metal nanoparticles according to any one of claims 1 to 6, R １ Metal nanoparticles in which tert-butyl is present.

8. A metal nanoparticle according to any one of claims 1 to 7, wherein each five-membered ring of the metallocene is a ring of the formula defined above (CH ２ ) ｎ -XR ２ R ３ Metal nanoparticles, wherein the nanoparticles are substituted with at least one identical or different group represented by (where X is P), and the nanoparticles are arranged in the form of a network of different nanoparticles linked by the metallocene ligand.

9. A method for using metal nanoparticles according to any one of claims 1 to 8 as a catalyst for hydrogen recovery by hydrolysis or solvent decomposition of an amine borane compound or a hydrazine borane compound, wherein the solvent is preferably a polar hydrogen donor, more preferably an alcohol, and even more preferably methanol or ethanol.

10. A method for recovering hydrogen from an amine borane or hydrazine borane, comprising hydrolyzing or sorbolicing the amine borane or hydrazine borane in the presence of metal nanoparticles according to the method described in any one of claims 1 to 8.

11. A method of use according to claim 9, or a manufacturing method according to claim 10, wherein the amine borane is of formula NR ２ 'H-BH ３ or BH ３ -NR ２ '-(CH ２ ) ｍ -NR ２ '-BH ３ Represented as such, R' may be the same or different, H, C ５ ~C １０ An aryl group, preferably a phenyl group, or C １ ~C ３０ Preferably C １ ~C １０ , more comfortable C １ ~C ５ It represents a linear or branched, saturated or unsaturated alkyl group, where m is 1, 2, or 3, and preferably the amine borane is NH ３ -BH ３ (AB), NMeH ２ -BH ３ (Methylamine borane MeAB), NMe ２ H-BH ３ (Dimethylamine borane DMAB) or H ３ B-NH ２ CH ２ CH ２ NH ２ -BH ３ (Ethylenediamine bisborane EDAB), method of use or method of manufacture.

12. A use or method according to any one of claims 9 or 11, or a method according to any one of claims 10 to 12, wherein the solvent decomposition is performed using ethanol or methanol.

13. A method according to any one of claims 10 to 12, wherein the reaction is carried out in a temperature range of -90°C to 100°C, preferably -40°C to 80°C, more preferably 0°C to 30°C, and even more preferably 20°C.

14. A method according to any one of claims 10 to 13, further comprising the step of recycling the nanoparticles.

15. A method according to claim 14, wherein the recycling is carried out by recovering the nanoparticles and washing the recovered nanoparticles with a solvent used for hydrolysis or sorbolisis of amine borane or hydrazine borane.

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