Gaining insight into the catalytic dehydrogenation of hydrazine borane in water

Çakanyıldırım, Çetin; Petit, Eddy; Demirci, Umit B.; Moury, Romain; Petit, Jean‐Fabien; Xu, Qiang; Miele, Philippe

doi:10.1016/j.ijhydene.2012.08.032

Cited by 14 publications

(11 citation statements)

References 30 publications

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“…The effective gravimetric hydrogen storage capacities were therefore low (<0.5 wt%) and not realistic for practical applications. The highest capacity ever reported is 1.2 wt% for a H2O/N2H4BH3 molar ratio of 42, but in these conditions the selectivity of the Ni0.89Pt0.11 catalyst was negatively affected [47]. This reveals another issue to overcome with the catalyst used in this reaction: it has to be selective whatever the concentration of the borane.…”

Section: Hydrolysis Of the Bh3 Group And Dehydrogenation Of The N2h4 mentioning

confidence: 97%

“…The former reaction is at least 40 times faster. In fact, during the first step, when the BH3 groups are hydrolyzed, some of the N2H4 moieties interact with the catalytic surface and decompose [47,48]. The second regime of kinetics (i.e., dehydrogenation of N2H4) determines the total time that the dehydrogenation of hydrazine borane really needs.…”

Section: Hydrolysis Of the Bh3 Group And Dehydrogenation Of The N2h4 mentioning

confidence: 99%

“…With respect to the nickel-based bimetallic alloy nanoparticles, several metals were tested: Pt, Rh, Ru, Ir, Fe, Co and Pd [52,53]. Though very active and almost-100% hydrogen selective, the Pt-, Rh-and Ir-containing systems were found not to be stable after the first cycle because of nickel surface enrichment, explained by borate-induced segregation [47,52]. Nickel, like cobalt, strongly adsorbs borates via M-O-B bonds, leading to the catalyst deactivation [54][55][56].…”

Section: Hydrolysis Of the Bh3 Group And Dehydrogenation Of The N2h4 mentioning

confidence: 99%

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Hydrazine Borane and Hydrazinidoboranes as Chemical Hydrogen Storage Materials

Moury

Demirci

2015

Energies

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Abstract:Hydrazine borane N2H4BH3 and alkali derivatives (i.e., lithium, sodium and potassium hydrazinidoboranes MN2H3BH3 with M = Li, Na and K) have been considered as potential chemical hydrogen storage materials. They belong to the family of boron-and nitrogen-based materials and the present article aims at providing a timely review while focusing on fundamentals so that their effective potential in the field could be appreciated. It stands out that, on the one hand, hydrazine borane, in aqueous solution, would be suitable for full dehydrogenation in hydrolytic conditions; the most attractive feature is the possibility to dehydrogenate, in addition to the BH3 group, the N2H4 moiety in the presence of an active and selective metal-based catalyst but for which further improvements are still necessary. However, the thermolytic dehydrogenation of hydrazine borane should be avoided because of the evolution of significant amounts of hydrazine and the formation of a shock-sensitive solid residue upon heating at >300 °C. On the other hand, the alkali hydrazinidoboranes, obtained by reaction of hydrazine borane with alkali hydrides, would be more suitable to thermolytic dehydrogenation, with improved properties in comparison to the parent borane. All of these aspects are surveyed herein and put into perspective.

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Section: Hydrolysis Of the Bh3 Group And Dehydrogenation Of The N2h4 mentioning

confidence: 97%

Section: Hydrolysis Of the Bh3 Group And Dehydrogenation Of The N2h4 mentioning

confidence: 99%

Section: Hydrolysis Of the Bh3 Group And Dehydrogenation Of The N2h4 mentioning

confidence: 99%

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Hydrazine Borane and Hydrazinidoboranes as Chemical Hydrogen Storage Materials

Moury

Demirci

2015

Energies

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“…(10)], was reported for bimetallic catalysts such as Rh 4 Ni alloy nanoparticles, Ni 0.6 Pt 0.4 /nanoporous carbon, and Ni 0.58 Pt 0.42 /graphene . However, the release of H 2 is stepwise: the first step is the hydrolysis of the BH 3 group and the reaction is faster than the second step consisting of the dehydrogenation of the N 2 H 4 moiety (Figure ) . The latter reaction starts slowly at the beginning of the process, but ends some time after the former reaction because it takes more time (sluggish kinetics).…”

Section: Other Hydrolytic B(−n)−h Compoundsmentioning

confidence: 93%

About the Technological Readiness of the H₂ Generation by Hydrolysis of B(−N)−H Compounds

Demirci

2018

Energy Tech

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At the beginning of the new millennium, hydrolysis of sodium borohydride (NaBH4) was presented as a promising on‐board technology to generate H2 for light‐duty vehicles. Years later, other B(−N)−H compounds (e.g., lithium borohydride (LiBH4) and ammonia borane (NH3BH3)) emerged as attractive alternatives whereas NaBH4 was struggling with several issues jeopardizing its implementation. Actually, efforts in the research and development of H2 generation by hydrolysis of B(−N)−H compounds have been intensive since the advent of NaBH4 almost 20 years ago. There may be a question with respect to this: What is the technological readiness of the promising hydrolytic B(−N)−H compounds? This Review aims at providing relevant elements in response to this question. In the first part, the most mature B(−N)−H compounds are discussed at length. In the second part, a survey of all other candidates is proposed. It is concluded that NaBH4 is the best hydrolytic B(−N)−H compound for marketing on a broad scale, but there are still key challenges to address.

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“…On the other hand, HB is able to reduce these metal ions so that no other reducing agent is required for the formation of transition metal nanoparticles. 27,[36][37][38][39]41,42 This prompted us to convey an electrochemical study for understanding the difference in reducing ability of AB and HB, which might be due to their different redox potentials, in addition to the kinetic factors. Although such potential data are normally available from the cyclic voltammetric measurements, surprisingly, no such data is available for HB, while the redox potential of AB has been reported.…”

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confidence: 99%

Electrochemical Behavior of Hydrazine Borane in Methanol Solution

Özhava

Önal

Özkâr

2014

J. Electrochem. Soc.

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Electrochemical behavior of hydrazine borane (HB) was investigated on gold electrode in 0.5 M LiClO 4 solution in methanol using cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and chronoamperometry. Two irreversible peaks at 164 and 530 mV are attributed to direct electro-oxidation of HB on gold electrode in methanol. Both EIS results and CV data at different scan rates indicate a diffusion controlled electron transfer reaction. Furthermore, the Tafel slope (b = 0.191 V) and charge transfer coefficient (α = 0.69) were obtained for the HB oxidation at the gold/solution interface. A possible ECE (electrochemicalchemical-electrochemical) mechanism is proposed for the irreversible two electron transfer reaction. This mechanism was also confirmed by the results of Nicholson-Shain test. Additionally, diffusion coefficient of HB was found to be 1.6 × 10 −5 cm 2 .s −1 using chronoamperometry. First oxidation peak of HB appears at a lower potential than that of ammonia borane (AB), clearly indicating that HB is a stronger reducing agent as compared to AB in methanol solution.The use of hydrogen as energy carrier is expected to facilitate the transition from fossil fuels to the renewable energy sources, on the way toward a sustainable energy future. 1,2 However, the development of an efficient method for the hydrogen storage is still a key issue in hydrogen economy. 3 Consequently, many efforts have been devoted to searching for chemical materials possessing high gravimetric hydrogen density suitable for both portable and stationary applications of hydrogen supply. 4-13 Among the several types of chemical hydrogen storage materials, boron-based hydrides have recently attracted great attention due to their high hydrogen content, safe storability, and easy H 2 release under mild conditions. 14 Although alkaline borohydrides, especially sodium salt, have been used in fuel cells as fuel, formation of BH 3 (OH) − during the oxidation in alkaline medium lowers the fuel cell efficiency. 15 Therefore, a number of studies have been conducted to minimize its formation. Gyenge has reported that BH 3 (OH) − formation can be eliminated in the presence of thiourea on Pt electrodes. 16 Electrooxidation of sodium borohydride on Au and Ag electrodes has been investigated by Chatenet et al. 17 and it has been reported that BH 3 (OH) − is oxidized at a lower potential than that of BH 4 − . Ç elikkan et al. 18 have reported that among various electrodes Au was the most active for the oxidation of BH 4 − in alkaline medium; on the other hand, Ni was found to be silent. The role of electrode material in the oxidation of BH 4 − in alkaline medium has also been investigated by Abruna et al. 19 and it has been noted that Pt shows better performance for direct borohydride applications as compared to Au. Formation of intermediate species, together with H 2 , during the oxidation of BH 4 − has been investigated by Ticianelli and coworkers via in situ FTIR and on-line Differential Electrochemical Mass Spectrometry. 20 Ammonia borane ...

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Gaining insight into the catalytic dehydrogenation of hydrazine borane in water

Cited by 14 publications

References 30 publications

Hydrazine Borane and Hydrazinidoboranes as Chemical Hydrogen Storage Materials

Hydrazine Borane and Hydrazinidoboranes as Chemical Hydrogen Storage Materials

About the Technological Readiness of the H₂ Generation by Hydrolysis of B(−N)−H Compounds

Electrochemical Behavior of Hydrazine Borane in Methanol Solution

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Gaining insight into the catalytic dehydrogenation of hydrazine borane in water

Cited by 14 publications

References 30 publications

Hydrazine Borane and Hydrazinidoboranes as Chemical Hydrogen Storage Materials

Hydrazine Borane and Hydrazinidoboranes as Chemical Hydrogen Storage Materials

About the Technological Readiness of the H2 Generation by Hydrolysis of B(−N)−H Compounds

Electrochemical Behavior of Hydrazine Borane in Methanol Solution

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Product

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About the Technological Readiness of the H₂ Generation by Hydrolysis of B(−N)−H Compounds