Hydrogen generation from the dehydrogenation of ammonia–borane in the presence of ruthenium(III) acetylacetonate forming a homogeneous catalyst

Duman, Sibel; Ozkar, Scrim

doi:10.1016/j.ijhydene.2012.10.041

Cited by 23 publications

(6 citation statements)

References 45 publications

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“…Air stable CAAC-Cu (CAAC = cyclic alkyl amino carbene) complex ( 4 ) has recently been reported by Bertrand exhibiting high (8400 mol H2 mol cat –1 h –1 ) TOFs at ambient reaction conditions using an acetone–water (80–20 wt %) organic solvent mixture (Scheme ). Although cobalt, − copper, iron, , and nickel − catalysts are often preferred over the noble metal catalysts due to their lower costs, the noble metal catalysts are showing often significantly higher activities making them economically competitive alternatives. ,,,− The most investigated noble-metal-containing catalysts rendering exceptional activities include rhodium- , and ruthenium-based systems . Although rhodium has shown the highest AB dehydrogenation activity so far, , its exceptionally higher price (more than 30 times compared to ruthenium) poses limits on their commercial application…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Ammonia Borane Hydrolytic Dehydrogenation in Neat Water Using Phase-Labeled CAAC-Ru Catalysts

Nagyházi

Turczel

Anastas

2020

ACS Sustainable Chem. Eng.

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Ammonia borane (AB) has received extensive attention in recent years as an emerging hydrogen storage material due to its high hydrogen density (19.6 wt %), nontoxicity, stability, and water solubility. Although AB itself is stable in water, its catalytic dehydrogenation (2 mol eq) in aqueous media produces borazine whose tandem hydrolytic reaction enables further hydrogen release (1 mol eq). Thus, water serves both as a reaction medium and also a pure hydrogen fuel source (33% of overall released H2). A high capacity and fast homogeneous AB hydrolytic dehydrogenation system is reported using water-soluble CAAC-Ru carbene catalysts (5 and 6). Applying catalyst 6 at 50 ppm (0.015 mM) loading a high TON of 43,600 can be observed; meanwhile, the yield of the released H2 remains high (73%, equal to 2.2 released molH2/molBH3NH3). The evolved hydrogen can achieve 2.9 molH2/molBH3NH3 ([6] = 3.0 mM) and a TON of 86,100 (equal to 1.70 kg H2 (released)/g Ru metal (used)) (10 ppm loading, [6] = 0.003 mM). The energy density of 1.70 kg H2 is equal to that of 6.6 L of gasoline, which is a general consumption for a medium category car/100 km. The reaction yields nonhazardous borates up to 99% yield, which are considered as a recyclable commodity material for hydrogen storage systems. As the metaborate ion (BO2 –)-induced catalyst passivation causing a decrease in accessibility of active sites in heterogeneous catalysis does not occur at homogeneous conditions, the reported high TON values can be achieved within significantly shorter reaction times and lower catalyst concentrations.

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Section: Introductionmentioning

confidence: 99%

Highly Efficient Ammonia Borane Hydrolytic Dehydrogenation in Neat Water Using Phase-Labeled CAAC-Ru Catalysts

Nagyházi

Turczel

Anastas

2020

ACS Sustainable Chem. Eng.

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“…The former, promoted by several metallic nanoparticles or clusters [6][7][8] and organometallic complexes (i.e. based on Rh, 9,10 Ru, [11][12][13] Ir, 14,15 Os, 16 Fe 8 or Pd 17 ), generates one equivalent of H 2 per mole of substrate and the AB ends up in the form of [H 2 B-NH 2 ] n oligomeric or polymeric materials (eqn (1)). Only some Ru nanoclusters 13 and two homogeneous catalysts based on Ru [18][19][20] and Ni 21 are able to further dehydrogenate the formed polyaminoboranes generating up to 2.8 equiv.…”

Section: Introductionmentioning

confidence: 99%

A readily accessible ruthenium catalyst for the solvolytic dehydrogenation of amine–borane adducts

et al. 2014

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The use of the readily available complex [Ru(p-Cym)(bipy)Cl]Cl as an efficient and robust precatalyst for homogeneously catalysed solvolysis of amine-borane adducts to liberate the hydrogen content of the borane almost quantitatively is being presented. The reactions can be carried out in tap water, and in aqueous mixtures with non-deoxygenated solvents. The system is also efficient for the dehydrocoupling of dimethylamine-borane under solvent-free conditions.

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“…For these systems the preferred transition metals are those from the second and third transition series, ruthenium, rhodium, palladium and platinum [43][44][45][46][47][48]. Ruthenium complexes used as catalysts have adequate charge density [44], and several strategies for their synthesis have been proposed.…”

Section: Synthesis and Characterization Of Ruthenium(ii) Complexes Inmentioning

confidence: 99%

Synthesis and characterization of ruthenium(II) complexes incorporating 4′-phenyl-terpyridine and triphenylphosphine

Moya

López

Pérez-Zúñiga

et al. 2015

Journal of Coordination Chemistry

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The syntheses of two new series of ruthenium(II) complexes incorporating substituted 4′-phenylterpyridine, triphenylphosphine and chloride (A Series) or hydride (B Series) are reported. In both series 4′-phenyl-terpyridine incorporated substituents of varying electronic character at the 4-position: 4`-(4-chlorophenyl)-2,2´:6´,2``-terpyridine (ClPh-tpy); 4`-(4-nitrophenyl)-2,2´:6´,2``-terpyridine (NO 2 Ph-tpy) and 4`-(4-methoxyphenyl)-2,2´:6´,2``-terpyridine (OMePh-tpy). The complexes have been characterized by elemental analysis and UV-Vis, IR and NMR spectroscopy and their electrochemical properties studied. The substituents on the 4′-phenylterpyridine ligand influence the properties of the metal center. For all complexes prepared, λ max of a characteristic low energy band in the UV-Vis spectrum was found to move to shorter wavelengths as the solvent polarity increased (a hypsochromic shift). For the B series complexes, the low energy band was broader and undergoes a small shift to lower frequencies as a result of the substitution of chloride by a hydride. The 1 H-and 31 P-NMR spectra clearly indicate that the geometry of the 4′-phenyl-terpyridine ligand is meridional in the complexes, with the two triphenylphosphines trans to each other. Upon optimization of the experimental procedures the yields increased to 70% for the B series complexes.

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Hydrogen generation from the dehydrogenation of ammonia–borane in the presence of ruthenium(III) acetylacetonate forming a homogeneous catalyst

Cited by 23 publications

References 45 publications

Highly Efficient Ammonia Borane Hydrolytic Dehydrogenation in Neat Water Using Phase-Labeled CAAC-Ru Catalysts

Highly Efficient Ammonia Borane Hydrolytic Dehydrogenation in Neat Water Using Phase-Labeled CAAC-Ru Catalysts

A readily accessible ruthenium catalyst for the solvolytic dehydrogenation of amine–borane adducts

Synthesis and characterization of ruthenium(II) complexes incorporating 4′-phenyl-terpyridine and triphenylphosphine

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