METHOD FOR STORING HYDROGEN

Abstract

Disclosed is the application of alkoxyamine-borane complexes for the storage of hydrogen.

Claims

1-13. (canceled)

14. A method for storing hydrogen, comprising providing and applying an effective amount of alkoxyamine-borane complexes.

15. The method according to claim 14, wherein the application of alkoxyamine-borane complexes for storing hydrogen is followed by a step of release of hydrogen.

16. The method according to claim 14, wherein the alkoxyamine-borane complexes are alkoxyamine-boranes of formula (I), ##STR00019## wherein R and R are independently selected from hydrogen, C.sub.1 to C.sub.10-alkyl or C.sub.3 to C.sub.10-cycloalkyl group.

17. A method for releasing hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes.

18. The method for releasing hydrogen according to claim 17, comprising a step of contacting of at least one alkoxyamine-borane complex with a catalyst, or step of thermal heating of the abovementioned alkoxyamine-borane complexes.

9. The method for releasing hydrogen according to claim 7, comprising a step of contacting at least one alkoxyamine-borane complex with a rhodium, platinum, palladium, gold or nickel complex.

20. The method for releasing hydrogen according to claim 17, comprising a step of contacting at least one alkoxyamine-borane complex with a complex chosen from RhCl(PPh.sub.3).sub.3, NiCl.sub.2(PPh.sub.3).sub.2, Rh@TBAB and Ni@TBAB, Pd(OH).sub.2/C, PtCl.sub.2, PdCl.sub.2, KAuCl.sub.4, Pt(PPh.sub.3).sub.4.

21. The method for releasing hydrogen according to claim 17, comprising a step of contacting of an alkoxyamine-borane complex with RhCl (PPh.sub.3).sub.3.

22. The method for releasing hydrogen according to claim 17, comprising a step of contacting of an alkoxyamine-borane complex with NiCl.sub.2(PPh.sub.3).sub.2.

23. The method for releasing hydrogen according to claim 17, comprising a step of contacting of an alkoxyamine-borane complex with Rh@TBAB.

24. The method for releasing hydrogen according to claim 17, comprising a step of contacting of an alkoxyamine-borane complex with Ni@TBAB.

25. The method for releasing hydrogen according to claim 17, comprising a step of thermal heating of the above-mentioned alkoxyamine-borane complexes above 80 C.

26. The method for releasing hydrogen according to claim 17, comprising a step of thermal heating of the above-mentioned alkoxyamine-borane complexes above 120 C.

27. A method for preparing alkoxyamine-borane complexes of formula (I) comprising a step of bringing together hydroxylamines of formula (II), ##STR00020## wherein R and R are selected from hydrogen, a C.sub.1 to C.sub.10-alkyl or C.sub.3 to C.sub.10-cycloalkyl group, or a salt thereof, with NaBH.sub.4 and a mineral acid, said method not requiring a purification step.

28. The method for preparing alkoxyamine-borane complexes according to claim 27, wherein the salt is a hydrochloride salt.

29. The method for preparing alkoxyamine-borane complexes according to claim 27, wherein the mineral acid is H.sub.2SO.sub.4 or HCl.

30. The method of preparation according to claim 27, of the following alkoxyamine-borane complexes: ##STR00021## comprising a step of bringing together respectively the following hydroxylamine hydrochlorides: ##STR00022## and NaBH.sub.4 and a mineral acid, this method does not require purification step.

31. The method of preparation according to claim 27, of the following alkoxyamine-borane complexes: ##STR00023## comprising a step of bringing together respectively the following hydroxylamine hydrochlorides: ##STR00024## and NaBH.sub.4 and a mineral acid chosen from H.sub.7SO.sub.4 or HCl, said method not requiring a purification step.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG. 1 relates to the study of the rate of dehydrogenation of complex (5) in the presence of 5 mol % of Wilkinson catalyst with on the x-axis the time expressed in minutes and on the y-axis the evolution of the gas volume expressed in cm.sup.3.

[0038] FIG. 2 relates to the study of the rate of dehydrogenation of complex (2) in the presence of 5 mol % of Wilkinson's catalyst with on the x-axis the time expressed in minutes and on the y-axis the evolution of the gas volume expressed in cm.sup.3.

[0039] FIG. 3 relates to the study of the rate of dehydrogenation of complex (5) in the presence of 5 mol % of NiCl.sub.2(PPh.sub.3).sub.2 with on the x-axis the time expressed in minutes and on the y-axis the evolution of the gas volume expressed in cm.sup.3.

[0040] FIG. 4 relates to the study of the rate of dehydrogenation of complex (5) in the presence of 5 mol % of Pt(PPh.sub.3).sub.4 with on the x-axis the time expressed in minutes and on the y-axis the evolution of the gas volume expressed in cm.sup.3.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Examples Relating to the Preparation of Alkoxyamine-Borane Complexes

Example 1

[0041] Tests carried out by the inventors to synthesize an alkoxyamine-borane complex from N,O-dimethylhydroxyhamine in the presence only of NaBH.sub.4 in THF resulted in a good yield of 77% in 2 hours.

##STR00007##

[0042] Optimization work on this synthesis (Table I) provided access to a yield of 86%. The results show that the optimum ratio between the alkoxyamine.Math.HCl and NaBH.sub.4 is 1:1.2. The obtained complex does not require purification.

TABLE-US-00001 TABLE 1 [00008] NaBH.sub.4 Temperature Time Reference (eq.) ( C.) (h) Treatment Yield (%) CF32dry 2 70 72 NaHCO.sub.3/DCM 6.5 CF35 2 RT 48 NaHCO.sub.3/DCM 76 CF65 1.6 RT 24 NaHCO.sub.3/DCM 64 CF651 1.2 70 24 NaHCO.sub.3/DCM 86 CF673 1.2 70 24 NaHCO.sub.3/DCM 63 CF652 1.2 RT 24 NaHCO.sub.3/DCM 51 CF653 2 RT 24 NaHCO.sub.3/DCM 79 CF6541 1.2 RT 2 NaHCO.sub.3/DCM 68 CF6542 1.2 RT 2 H.sub.2O/EtOAc 77

Example 2

[0043] The alkoxyamine-borane complex (2) was synthesized under the same conditions as above, using O-tert-butylhydroxylamine hydrochloride in the presence of sodium borohydride in THE (Table 2). This synthesis was first performed on a small scale (CF39) and then on a larger scale (CF452).

TABLE-US-00002 TABLE 2 [00009] NaBH.sub.4 Temperature Time Reference (eq.) ( C.) (h) Treatment Yield (%) CF39 2 RT 24 NaHCO.sub.3/DCM 38 CF452 2 RT 24 NaHCO.sub.3/DCM 64 CF522 1.3 RT 24 NaHCO.sub.3/DCM 48

Examples 3 and 4

[0044] Unlike previous syntheses, the alkoxyamine-borane complexes (3) and (4) were prepared from non-commercial hydrochlorides (Tables 3, 4 and 5) which therefore had to be synthesized beforehand.

TABLE-US-00003 TABLE 3 [00010] Temperature Time Reference NaBH.sub.4 (eq.) ( C.) (h) Treatment Yield (%) CF77 1.2 RT 24 H.sub.2O/Et.sub.2O 37.6 CF80 1.2 RT 24 H.sub.2O/Et.sub.2O 35

TABLE-US-00004 TABLE 4 [00011] Temperature Time Reference NaBH.sub.4 (eq.) ( C.) (h) Treatment Yield (%) CF89 1.2 RT 24 H.sub.2O/Et.sub.2O 65 CF97 1.2 RT 24 H.sub.2O/Et.sub.2O 18

Example 5

[0045] The last alkoxyamine-borane complex that was synthesized is O-methylhydroxylamine-borane (5) from the commercial O-methylhydroxylamine hydrochloride in the presence of NaBH.sub.4 in THE. Unlike the other starting materials, this hydrochloride has low solubility in most solvents. For this synthesis, significant work on optimizing the conditions has been performed in order to improve the solubility of O-methylhydroxylamine hydrochloride (Table 5).

TABLE-US-00005 TABLE 5 [00012] NaBH.sub.4 Temperature Time Yield Comments/ Reference (eq.) ( C.) (h) Treatment (%) Modifications CF44 2 RT 24 NaHCO.sub.3/DCM 21 CF462 2 RT 24 NaHCO.sub.3/DCM 10 CF53 1.25 RT 24 NaHCO.sub.3/DCM 17 CF571 1.2 70 24 NaHCO.sub.3/DCM 18 CF645 1.2 70 24 NaHCO.sub.3/DCM 7 Sonication 1 h CF648 1.2 RT 24 H.sub.2O/Et.sub.2O 47 Dehydrogenation (20 ml of gas formed) CF64EtA 1.2 RT 24 H.sub.2O/Et.sub.2O 12 Solvent: THF/EtOAc CF64EtA2 2 RT 24 H.sub.2O/Et.sub.2O 28 Solvent: THF/EtOAc/EtOH CF64De2 1.2 30 24 H.sub.2O/Et.sub.2O 43 Dehydrogenation (15 ml of 40 mL of expected gas) CF641eq 1 30 24 H.sub.2O/Et.sub.2O 44 CF642eq 2 30 24 H.sub.2O/Et.sub.2O 246 Difficulties in drying the product CF64H2O 1.2 30 24 H.sub.2O/Et.sub.2O 64 Solvent: THF/H.sub.2O CF64H2O1 1.2 30 24 H.sub.2O/Et.sub.2O 53 Excess THF CF64H2O2 1.2 30 24 H.sub.2O/Et.sub.2O 46 Less THF CF64H2O3 1.2 30 24 H.sub.2O/Et.sub.2O 17 Fast addition of a MeONH.sub.3.sup.+Cl.sup./H.sub.2O solution CF64H2O4 1.2 30 24 H.sub.2O/Et.sub.2O 14 Dropwise addition of a MeONH.sub.3.sup.+Cl.sup./H.sub.2O solution CF64H2O5 1.2 30 72 H.sub.2O/Et.sub.2O 20 NaBH.sub.4 added last CF64H2O6 1.2 30 24 H.sub.2O/Et.sub.2O 26 NaBH.sub.4 added last CF64H2O7 1.2 30 24 H.sub.2O/Et.sub.2O 44 Saturated solution of MeONH.sub.3.sup.+Cl.sup./H.sub.2O CF64H2O8 1.2 30 24 H.sub.2O/Et.sub.2O 39 Diluted solution of MeONH.sub.3.sup.+Cl.sup./H.sub.2O

[0046] Examples related to the dehydrogenation of alkoxyamine-borane complexes:

[0047] Much research has been conducted on the alkoxyamine-borane complexes (1), (2) and (5). These experiments allowed to identify the interesting properties of the boron-nitrogen dative bond. The goal of these experiments was thus to establish the usefulness of these compounds as precursors in some reactions, for example in the formation of aminoboranes by dehydrogenation.

[0048] In addition, the alkoxyamin -borate complexes show strong potential for hydrogen storage applications because of their high density of hydrogen.

[0049] The dehydrogenation of the above-mentioned alkoxyamine-borane complexes in the presence of transition metal catalysts is described herein.

Example 6

[0050] The most effective catalysts have been found to be Wilkinson's catalyst (RhCl(PPh.sub.3).sub.3) and NiCl.sub.2(PPh.sub.3).sub.2 with which one equivalent of hydrogen was released from each alkoxyamine-borane complex (Tables 6, 7 and 8).

TABLE-US-00006 TABLE 6 [00013] Time Catalyst Temperature ( C.) (min) Volume of formed gas (cm.sup.3) PdCl.sub.2dppp 70 40 20 Pd(OAc).sub.2 70 85 36 Pd(OH).sub.2/C 70 540 1.5 NiCl.sub.26H.sub.2O 70 1440 6 RuCl.sub.2xH.sub.2O 30 PtCl.sub.2 30-50 900 20 RhCl(PPh.sub.3).sub.3 30 7 22 NiCl.sub.2(PPh.sub.3).sub.3 30 29 22 PdCl.sub.2 30 47 22 CuI 30 K(AuCl.sub.4) 30 69 8 Pt(PPh.sub.3).sub.4 30-70 204 14

Examples 7 and 8

[0051]

TABLE-US-00007 TABLE 7 [00014] [00015] Time Catalyst Temperature ( C.) (min) Volume of formed gas (cm.sup.3) Pd(OAc).sub.2 30-70 Pd(OH).sub.2/C 30-70 900 5.5 PtCl.sub.2 30-70 900 8 RhCl(PPh.sub.3).sub.3 30 12 8.5 NiCl.sub.2(PPh.sub.3).sub.3 40 11.20 10 PdCl.sub.2 70 47.50 22

TABLE-US-00008 TABLE 8 [00016] Temperature Time Volume of Catalyst ( C.) (min) formed gas (cm.sup.3) Pd(OAc).sub.2 50-80 900 9 Pd(OH).sub.2/C 60-80 1050 8 PtCl.sub.2 (in THF) 50 900 10 RhCl(PPh.sub.3).sub.3 (2.5 mol %) 50 15 10 NiCl.sub.2(PPh.sub.3).sub.3 30-50 36 12

[0052] The comparison of the decomposition rates of the three alkoxyamine-borane complexes (1), (2) and (5) clearly shows that the N,O-dimethylhydroxylarnine-borane (1) is the least stable of the three.

[0053] The complexes (1), (2) and (5) have different dehydrogenation speeds, the use of either of these complexes thus makes it possible to modulate the speed of dehydrogenation.

Example 9

[0054] Additional tests were carried out on the O-methylhydroxylamine-borane complex (5) with Wilkinson's catalyst (RhCl(PPh.sub.3).sub.3), NiCl.sub.2(PPh.sub.3).sub.2 and the corresponding nanocatalysts at 50 C. (Table 9).

[0055] The two nanocatalysts have emerged as effective in the dehydrogenation reaction of O-methylhydroxylamine-borane (5).

TABLE-US-00009 TABLE 9 [00017] [00018] Temperature Volume of Catalyst ( C.) Time (min) formed gas (cm.sup.3) RhCl(PPh.sub.3).sub.3 50-80 3 10 NiCl.sub.2(PPh.sub.3).sub.3 60-80 6 9 Rh@TBAB 50 37 15 Ni@TBAB 50 900 11 RhCl(PPh.sub.3).sub.3 60 108 15.5 (additional 1 mol %)