Hydrogen liberation from the hydrolytic dehydrogenation of dimethylamine-borane at room temperature by using a novel ruthenium nanocatalyst

Caliskan, Salim
Zahmakıran, Mehmet
Özkar, Saim
Herein we report the discovery of an in situ generated, highly active nanocatalyst for the room temperature dehydrogenation of dimethylamine-borane in water. The new catalyst system consisting of ruthenium(0) nanoparticles stabilized by the hydrogenphosphate anion can readily and reproducibly be formed under in situ conditions from the dimethylamine-borane reduction of a ruthenium(III) precatalyst in tetrabutylammonium dihydrogenphosphate solution at 25 +/- 0.1 degrees C. These new water dispersible ruthenium nanoparticles were characterized by using a combination of advanced analytical techniques. The results show the formation of well-dispersed ruthenium(0) nanoparticles of 2.9 +/- 0.9 nm size stabilized by the hydrogenphosphate anion in aqueous solution. The resulting ruthenium(0) nanoparticles act as a highly active catalyst in the generation of 3.0 equiv. of H-2 from the hydrolytic dehydrogenation of dimethylamine-borane with an initial TOF value of 500 h(-1) at 25 +/- 0.1 degrees C. Moreover, they provide exceptional catalytic lifetime (TTO = 11 600) in the same reaction at room temperature. The work reported here also includes the following results; (i) monitoring the formation kinetics of the in situ generated ruthenium nanoparticles, by using the hydrogen generation from the hydrolytic dehydrogenation of dimethylamine-borane as a catalytic reporter reaction, shows that sigmoidal kinetics of catalyst formation and concomitant dehydrogenation fits well to the two-step, slow nucleation and then autocatalytic surface growth mechanism, A -> B (rate constant k(1)) and A + B -> 2B (rate constant k(2)), in which A is RuCl3 center dot 3H(2)O and B is the growing, catalytically active Ru(0)(n) nanoclusters. (ii) Hg(0) poisoning coupled with activity measurements after solution infiltration demonstrates that the in situ generated ruthenium(0) nanoparticles act as a kinetically competent heterogeneous catalyst in hydrogen generation from the hydrolytic dehydrogenation of dimethylamine-borane. (iii) A compilation of kinetic data depending on the temperature and catalyst concentration is used to determine the dependency of reaction rate on catalyst concentration and the activation energy of the reaction, respectively.


Üner, Deniz; GERSTEIN, BC; KING, TS (Elsevier BV, 1994-04-01)
The interaction of hydrogen on potassium promoted catalysts prepared by both sequential and co-impregnation methods was studied by proton NMR spectroscopy. Potassium addition decreased the amounts of both hydrogen adsorbed on the metal (site blocking) and the support hydroxyl groups. No evidence for a ruthenium-mediated (through-metal) electronic interaction between potassium species and adsorbed hydrogen was found. During catalyst preparation, potassium was incorporated on the support by an exchange with t...
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Celik, Derya; Karahan, Senem; Zahmakiran, Mehmet; Özkar, Saim (2012-03-01)
Herein, we report the preparation and characterization of rhodium(0) nanoparticles supported on hydroxyapatite (Ca-10(OH)(2)(PO4)(6), HAP) and their catalytic use in the hydrolysis of hydrazine-borane, which attracts recent attention as promising hydrogen storage materials. Hydroxyapatite supported rhodium(0) nanoparticles were readily prepared by the hydrazine-borane reduction of rhodium(III)-exchanged hydroxyapatite in situ during the hydrolysis of hydrazine-borane at room temperature. Characterization of...
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Eroglu, AE; Volkan, Mürvet; Bayramh, E; Ataman, Osman Yavuz; Mark, HB (1996-07-01)
In the analytical system suggested, atmospheric hydrogen sulfide reacts with the surface of a filter paper treated with aqueous cadmium chloride and yields a luminescent species whose intensity can be correlated with the analyte concentration in ambient air. It was shown that the luminescent species are CdS solid particles which were formed in a well defined size. The paper luminescence was also tried on polymeric surfaces; polyethyleneoxide, polyvinyl alcohol, ethylcellulose and carboxymethylcellulose were...
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Hydrogen productivity of photosynthetic bacteria on dark fermenter effluent of potato steam peels hydrolysate
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Hydrogen productivities of different photosynthetic bacteria have been searched on real thermophilic dark fermentation effluents (DFE). The results obtained with potato steam peels hydrolysate (PSP) DFE were compared to glucose DFE. Photobiological hydrogen production has been carried out in indoor, batch photobioreactors using several strains of purple non-sulfur (PNS) bacteria such as Rhodobacter capsulatus (DSM1710), Rhodobacter capsulatus hup- (YO3), Rhodobacter sphaeroides O.U.001 (DSM5864), Rb. sphaer...
Citation Formats
S. Caliskan, M. Zahmakıran, F. DURAP, and S. Özkar, “Hydrogen liberation from the hydrolytic dehydrogenation of dimethylamine-borane at room temperature by using a novel ruthenium nanocatalyst,” DALTON TRANSACTIONS, pp. 4976–4984, 2012, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/40642.