Oleylamine-stabilized ruthenium(0) nanoparticles catalyst in dehydrogenation of dimethylamine-borane
Graphical abstract
Introduction
The safe and efficient storage of hydrogen is the key in the hydrogen based energy policies [1], [2]. There has been rapidly growing interest for the development of hydrogen storage materials with high volumetric and gravimetric capacity [3]. Boron–nitrogen compounds such as NH3BH3 [4], NR3BH3 [5], NH3B3H7 [6], NH4B3H8 [7], N2H4BH3 [8], have been considered as solid hydrogen storage materials as they have high gravimetric hydrogen storage capacity and inclination for bearing protic (N–H) and hydridic (B–H) hydrogen, which can be discharged and recharged in different chemical processes [9].More importantly, recent reports related to the regeneration of dehydrogenation products reveal the importance of the catalytic dehydrogenation of amine-borane adducts [10], [11].Of particular importance, dimethylamine-borane ((CH3)2NHBH3, DMAB) [12],which has been considered as solid hydrogen storage materials [13], [14], can release hydrogen either by hydrolysis in aqueous solution [15], [16] or dehydrogenation in organic medium [17], [18]. Recent studies show that the catalytic dehydrocoupling of dimethylamine-borane potentially releases up to 3.5 wt% H2 (Equation (1)) [19], [20].
A number of catalysts have recently been developed to improve the rate of H2 elimination from dimethylamine-borane: Rhodium colloids or complexes [21], [22], [23], [24], [25], [26], [27], [28], [29], rhodium(0) nanoparticles [18], [30], [31], ruthenium(0) nanoparticles or complexes [32], [33], [34], rhenium complexes [35], nickel complexes [36], [37], titanocene compounds [38], [39], [40], [41], titanium and zirconium sandwich complexes [40], [42], [43], metal carbonyls [44].While the highest catalytic activity has been achieved by using homogeneous [η5-C5H3-1,3-(SiMe3)2Ti]2 catalyst [43] in dehydrogenation of dimethylamine-borane, herein we report a semi heterogeneous ruthenium(0) nanoparticles catalyst with the highest activity and longest life-time in the same reaction at room temperature. Ruthenium(0) nanoparticles were in situ formed from the reduction of ruthenium(III) chloride by dimethylamine borane and stabilized by oleylamine (OAm). This is the first example of using OAm as stabilizer for the ruthenium(0) nanoparticles and employing them as catalysts in the dehydrogenation of dimethylamine-borane. The OAm-stabilized ruthenium(0) nanoparticles show catalytic activity higher than the heterogeneous catalysts reported for the dehydrogenation of dimethylamine-borane [32], [33].They provide an initial turnover frequency of 137 h−1 in generation of 1 equivalent H2 per mole of dimethylamine-borane (Me2NHBH3) which is converted to cyclic aminoborane ([Me2NBH2]2). Our report also includes the results of kinetic study on the hydrogen generation from the dehydrogenation of dimethylamine-borane catalyzed by OAm-stabilized ruthenium(0) nanoparticles depending on the catalyst concentration, substrate concentration, and temperature as well as the activation parameters (Ea, ΔH# and ΔS#) of catalytic dehydrogenation of dimethylamine-borane calculated from the kinetic data. Further experiments performed to determine the catalytic lifetime showed that OAm-stabilized ruthenium(0) nanoparticles provide 20,660 turnovers in hydrogen generation from the dehydrogenation of dimethylamine-borane at room temperature. Moreover, the OAm-stabilized ruthenium(0) nanoparticles exhibit high durability throughout their catalytic use in the dehydrogenation reaction against agglomeration and previously unprecedented reusability in the dehydrogenation of dimethylamine-borane.
Section snippets
General and materials
All commercially obtained chemicals were used as received unless indicated otherwise. Carbon disulfide (CS2), oleylamine (cis-1-amino-9-octadecene, OAm), ruthenium(III) chloride (RuCl3), dimethylamine-borane and toluene were purchased from Sigma–Aldrich®. Toluene was distilled over sodium under nitrogen atmosphere for 12 h. All glassware and Teflon-coated magnetic stir bars were washed with acetone and copiously rinsed with distilled water before drying in an oven at 150 °C.
Equipment
The dehydrogenation
In situ formation of oleylamine-stabilized ruthenium(0) nanoparticles and concomitant catalytic dehydrogenation of dimethylamine-borane
Formation of ruthenium(0) nanoparticles from the reduction of ruthenium(III) chloride by dimethylamine-borane and dehydrogenation of dimethylamine-borane occur concomitantly in the same reactor. In a typical experiment, for example, performed by starting with 2.0 mM ruthenium(III) chloride, 6.0 mM oleylamine and 200 mM dimethylamine-borane in 5.0 mL toluene at room temperature, the color of solution changes from orange to dark brown within less than 15 min, indicating the formation of
Conclusions
In summary, our study on the formation and characterization of OAm-stabilized ruthenium(0) nanoparticles catalyst in the dehydrogenation of dimethylamine-borane led to the following conclusions and insights:
- 1.
OAm-stabilized ruthenium(0) nanoparticles were reproducibly formed during the dehydrogenation of dimethylamine-borane starting with a commercially available precursor.
- 2.
That an increasing catalytic activity was observed after a certain period of time (induction time) in each case is indicative
Acknowledgments
Partial support by Turkish Academy of Sciences and Bingöl University Scientific Research Projects Unit is gratefully acknowledged.
References (49)
- et al.
Zeolite framework stabilized nickel(0) nanoparticles: active and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia-borane and sodium borohydride
Catal Today
(2011) - et al.
Catalytic hydrolysis of hydrazine borane for chemical hydrogen storage: highly efficient and fast hydrogen generation system at room temperature
Int J Hydrogen Energy
(2011) - et al.
Water dispersible acetate stabilized ruthenium(0) nanoclusters as catalyst for hydrogen generation from the hydrolysis of sodium borohyride
J Mol Catal A Chem
(2006) - US Department of Energy (DOE). Basic research needs for the hydrogen economy, report of the basic energy sciences...
Inter Academy Council (I.A.C.) report, lighting the way towards a sustainable energy futures
(2007)- et al.
Renewable hydrogen production
Int J Energy Res
(2008) - et al.
Amine- and phosphine-borane adducts: new interest in old molecules
Chem Rev
(2010) - et al.
Ammonia triborane: a promising new candidate for amineborane-based chemical hydrogen storage
J Am Chem Soc
(2006) - et al.
Ammonium octahydrotriborate (NH4B3H8): new synthesis, structure, and hydrolytic hydrogen release
Inorg Chem
(2011) - et al.
Recent developments on hydrogen release from ammonia borane
Mater Matt
(2007)
Efficient regeneration of partially spent ammonia borane fuel
Angew Chem Int Ed
Thermodynamic studies and hydride transfer reactions from a rhodium complex to BX3 compounds
J Am Chem Soc
Production of H2 from combined endothermic and exothermic hydrogen carriers
J Am Chem Soc
Ammonia-borane: the hydrogen source par excellence?
Dalton Trans
Ammonia-borane and related compounds as dihydrogen sources
Chem Rev
Structural characteristics and catalytic activities of nanocrystalline Ni-Mo-B coatings obtained by catalytic electroless reduction
Prot Met
Effect of doping nickel-boron alloys with rhenium, molybdenum, or tungsten on kinetics of partial reactions of chemical-catalytic reduction of metal ions
Russ J Elect
Scope and selectivity of heterogeneous rh-0-catalyzed tandem dehydrocoupling/hydrogenation using Me2NH center dot BH3 as a stoichiometric H-2 source
Eur J Org Chem
Dimethylammoniumhexanoate stabilized rhodium(0) nanoclusters identified as true heterogeneous catalysts with the highest observed activity in the dehydrogenation of dimethylamine-borane
Inorg Chem
Rhodium-catalyzed formation of boron-nitrogen bonds: a mild route to cyclic aminoboranes and borazines
Chem Commun
Transition metal-catalyzed formation of boron-nitrogen bonds: catalytic dehydrocoupling of amine-borane adducts to form aminoboranes and borazines
J Am Chem Soc
Poisoning of heterogeneous, late transition metal dehydrocoupling catalysts by boranes and other group 13 hydrides
J Am Chem Soc
Heterogeneous or homogeneous catalysis? Mechanistic studies of the rhodium-catalyzed dehydrocoupling of amine-borane and phosphine-borane adducts
J Am Chem Soc
Ambient temperature, tandem catalytic dehydrocoupling hydrogenation reactions using Rh colloids and Me2NH center dot BH3 as a stoichiometric H-2 source
J Am Chem Soc
Cited by (31)
Nanotitania supported ruthenium(0) nanoparticles as active catalyst for releasing hydrogen from dimethylamine borane
2024, International Journal of Hydrogen EnergyEco-friendly dehydrogenation of dimethylamine-borane catalyzed by core-shell-looking tri-metallic RuNiPd nanoclusters loaded on white-flowering horse-chestnut seed
2022, International Journal of Hydrogen EnergyCitation Excerpt :Various catalysts such as mono-metallic [35–37], bi-metallic [29,38,39] and tri-metallic [40,41] have been used to obtain hydrogen from DMAB by suitable methods. Materials such as oleylamine [42–44], nanotitania [45], poly vinyl pyrrolidone [33,46], poly (styrene-co-maleic anhydride) [33], alumina [33,47], zeolitic imidazolate framework [48], ceria [37,49,50], tungsten(VI) oxide [51], graphene oxide [17,52], 3-aminopropyltriethoxysilane [53,54], hydrogenphosphate anion [55], dimethylammonium hexanoate [56], 2-phosphinoaryloxide [57], ionic liquids [58–60], functionalized multiwalled carbon nanotube [61] are often used to stabilize or support these catalysts that catalyze the release of hydrogen from DMAB. As seen above, the majority of stabilizers used to stabilize catalysts are commercially purchased chemical materials.
Recent advances in soluble ruthenium(0) nanocatalysts and their reactivity
2020, Applied Catalysis A: GeneralRuthenium nanoparticles supported in the network of HES-p(AMPS) IPN hydrogel as efficient catalyst for hydrogen production from the hydrolysis of ethylenediamine bisborane
2020, International Journal of Hydrogen EnergyCitation Excerpt :Fig. 3(c) shows the powder XRD patterns for HES-p(AMPS) IPN and Ru@HES-p(AMPS) IPN catalyst. The broad peak at almost 2θ = 41.5 shows that the ruthenium particles in the Ru@HES-p(AMPS) IPN catalyst structure are in the (101) plane of a face centered cubic crystal structure (fcc) and their particle size is 10 nm or smaller [46]. This signal was observed to be very weak due to the low ruthenium content in the hydrogel network structure and particle sizes of 10 nm or less [12,16].
Transition metal nanoparticle catalysts in releasing hydrogen from the methanolysis of ammonia borane
2020, International Journal of Hydrogen Energy