Monodisperse nickel nanoparticles in the solvent-free dehydrogenation of dimethylamine borane

Demir, Hakan; Duman, Sibel

doi:10.1016/j.ijhydene.2015.06.093

Cited by 21 publications

(28 citation statements)

References 32 publications

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“…4,44 However, the metal-catalyzed-supported dehydrogenation of DMAB produces BN resonance at δ = 25.5 ppm. 16 5, whereas Figure 6 represents the 1 H NMR of DMAB/IL systems before and after dehydrogenation. From Figure 5i, the chemical shift of −BH 3 is assigned at δ = 1.45 ppm (denoted by "a3"), whereas the singlet spectrum at δ = 2.26 ppm (denoted by "b3") is assigned to the −CH 3 moiety.…”

Section: Resultsmentioning

confidence: 99%

“…A different set of intermediates and products were reported by Demir and Duman 16 It would be further useful to discuss and compare the ILfacilitated dehydrogenation route of other amine boranes. The ILs often suppress the induction period of amine boranes during dehydrogenation with a result that the process occurs at significantly reduced temperature.…”

Section: Resultsmentioning

confidence: 99%

“…The nickel nanocatalyst-supported dehydrogenation of DMAB produces dimethylamino diborane and bis(dimethylamino) borane. 16 The titanium-based catalyst also facilitates the formation of (H 2 BNMe 2 ) 2 and (Me 2 N) 2 BH with the formation of (CH 3 ) 2 NBH 2 and (CH 3 ) 2 N−BH 2 −N(CH 3 ) 2 −BH 2 intermediates. 24 Group 2 elements such as magnesium-and calcium-based catalysts undergo thermolysis of DMAB complexes at 60 °C and produce (H 2 BNMe 2 ) 2 as a major product with trace amount of (Me 2 N) 2 BH.…”

Section: Introductionmentioning

confidence: 99%

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Low- to Room-Temperature Dehydrogenation of Dimethylamine Borane Facilitated by Ionic Liquids: Molecular Modeling and Experimental Studies

2020

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A novel low-and room-temperature dehydrogenation of dimethylamine borane (DMAB) is being reported using hydrogen sulfate-based ionic liquids (ILs), namely, 1-ethyl-3-methylimidazolium hydrogen sulfate ([EMIM][HSO 4 ]) and 1-butyl-3methylimidazolium hydrogen sulfate ([BMIM][HSO 4 ]). The ILs are selected from a pool of potential ILs using a conductor-like screening model-segment activity coefficient (COSMO-SAC) model, and the dehydrogenation is performed at 0, 15, and 25 °C and a high vacuum of 4 × 10 −2 mbar gauge pressure. The dehydrogenated products are characterized with 1 H and 11 B NMR. 1 H NMR characterization reveals the structural integrity of ILs after the dehydrogenation. The 11 B NMR characterization reveals the evolution of −BH 2 and BN moieties during dehydrogenation. Based on the 11 B NMR study, the IL-assisted intramolecular and intermolecular dehydrogenation mechanism has been proposed. The intramolecular dehydrogenation pathway of dehydrogenation is proposed at 0 °C, and the intermolecular dehydrogenation pathway is at 15 and 25 °C. Formation of DMAB dimers has been confirmed for the intermolecular dehydrogenation pathway; on the contrary, DMAB does not oligomerize as other amine boranes. The interaction energy calculations reveal a greater stability of DMAB in [EMIM][HSO 4 ] than in [BMIM][HSO 4 ] IL. The anionic moiety of ILs is found to be the prominent pathway for the hydrogen bond interaction with protic and hydridic moieties of DMAB. It confirms the dominant role with respect to the selection of anion in hydrogen production.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Low- to Room-Temperature Dehydrogenation of Dimethylamine Borane Facilitated by Ionic Liquids: Molecular Modeling and Experimental Studies

2020

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“…However, efficient and reversible release of H 2 from DMAB requires a suitable catalyst . Many transition metals can catalyze the dehydrogenation of DMAB: [Ir(1,5‐cod)(μ‐Cl)] 2 , [Rh(1,5‐cod)(μ‐Cl)] 2 , Rh 0 /[N(oct) 4 ]Cl, [RhCl(PHCy 2 ) 3 ], Rh 0 nanoparticles (NPs), RhCl 3 , Pt 0 NPs/TBA, Pt 0 NPs/DPA@GO, Pt 0 NPs/AA, Pd 0 NPs/MOF, Ni 0 NPs, Cp 2 Ti, [η 5 ‐C 5 H 3 ‐1,3‐(SiMe 3 ) 2 Ti] 2 , Ru 0 NPs/OAm, Ru 0 NPs/APTS, [ReBr 2 (NO)(P i Pr 3 ) 2 (CH 3 CN)], [Ru(H)(PMe 3 )(N(C 2 H 4 P i Pr 2 ) 2 ], [(1‐methylborabenzene) 2 YR] …”

Section: Introductionmentioning

confidence: 99%

Oleylamine‐Stabilized Copper(0) Nanoparticles: An Efficient and Low‐Cost Catalyst for the Dehydrogenation of Dimethylamine Borane

Duman

Özkâr

2017

ChemCatChem

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Copper(0) nanoparticles, in situ generated from the reduction of copper(II) 2‐ethylhexanoate during the dehydrogenation of dimethylamine borane (DMAB) at 50.0±0.1 °C in toluene solution, are active catalysts in hydrogen generation from DMAB, but not very stable against agglomeration. Addition of 5.0 equivalents of oleylamine (OAm) was found to stabilize copper(0) nanoparticles noticeably, while maintaining high catalytic activity. Oleylamine‐stabilized copper(0) nanoparticles could be isolated from the solution and characterized by XRD, TEM, UV/Vis, attenuated total reflectance (ATR)‐FTIR, and 11B NMR spectroscopies. Our report also includes (i) comparative catalytic activities of copper(0) nanoparticles in the absence and presence of OAm depending on the initial [OAm]/[Cu] ratio, catalyst concentration, substrate concentration, and temperature, (ii) the catalytic lifetime of copper(0) nanoparticles in the absence and presence of OAm in the dehydrogenation of DMAB at 50.0±0.1 °C, (iii) testing the ease of isolation and reusability of copper(0) nanoparticles in the absence and presence of OAm in the dehydrogenation of DMAB, (iv) the results of quantitative kinetic poisoning experiments by using 1,10‐phenanthroline, showing that copper(0) nanoparticles are kinetically competent catalysts in the dehydrogenation of DMAB.

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“…However,e fficient and reversible release of H 2 from DMAB requires as uitable catalyst. [5] Many transition metals can catalyze the dehydrogenation of DMAB: [6] [Ir(1,5-cod)(m-Cl)] 2 , [5b] [Rh(1,5-cod)(m-Cl)] 2 , [5a] Rh 0 /[N(oct) 4 ]Cl, [7] [RhCl(PHCy 2 ) 3 ], [8] Rh 0 nanoparticles (NPs), [9] RhCl 3 , [4] Pt 0 NPs/TBA, [10] Pt 0 NPs/ DPA@GO, [11] Pt 0 NPs/AA, [12] Pd 0 NPs/MOF, [13] Ni 0 NPs, [14] Cp 2 Ti, [15] [h 5 -C 5 H 3 -1,3-(SiMe 3 ) 2 Ti] 2 , [5] Ru 0 NPs/OAm, [16] Ru 0 NPs/APTS, [17] [Re-Br 2 (NO)(PiPr 3 ) 2 (CH 3 CN)], [18] [Ru(H)(PMe 3 )(N(C 2 H 4 PiPr 2 ) 2 ], [7] [(1methylborabenzene) 2 YR]. [19] Although the highest catalytic activity is achieved by using the homogeneous catalyst [h 5 -C 5 H 3 -1,3-(SiMe 3 ) 2 Ti] 2 in the dehydrogenation of DMAB, [5] current researchh as shifted to the development of heterogeneous catalysts owing to the simple product separation and catalystr ecovery.…”

Section: Introductionmentioning

confidence: 99%

Oleylamine-stabilized ruthenium(0) nanoparticles catalyst in dehydrogenation of dimethylamine-borane

Duman¹,

Özkâr²

2013

International Journal of Hydrogen Energy

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Monodisperse nickel nanoparticles in the solvent-free dehydrogenation of dimethylamine borane

Cited by 21 publications

References 32 publications

Low- to Room-Temperature Dehydrogenation of Dimethylamine Borane Facilitated by Ionic Liquids: Molecular Modeling and Experimental Studies

Low- to Room-Temperature Dehydrogenation of Dimethylamine Borane Facilitated by Ionic Liquids: Molecular Modeling and Experimental Studies

Oleylamine‐Stabilized Copper(0) Nanoparticles: An Efficient and Low‐Cost Catalyst for the Dehydrogenation of Dimethylamine Borane

Oleylamine-stabilized ruthenium(0) nanoparticles catalyst in dehydrogenation of dimethylamine-borane

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