Metal-free, polyether-mediated H2-release from ammonia borane: roles of hydrogen bonding interactions in promoting dehydrogenation.
Polyetheral additives were found to be efficient promoters to enhance the rate of H2-release from ammonia borane (AB) at various temperatures. In particular, tetraethylene glycol dimethyl ether (T4EGDE, 29 wt% relative to AB + T4EGDE) exhibited significantly improved activities for AB dehydrogenation, with the material-based hydrogen storage capacity of 10.3 wt% at 125 °C within 40 min. In situ FT-IR spectroscopy indicated the formation of B-(cyclodiborazanyl)amino-borohydride (BCDB), borazine, and μ-aminodiborane as gaseous byproducts. In addition, (11)B nuclear magnetic resonance (NMR) spectroscopy further revealed that diammoniate of diborane (DADB) was initially formed to give polyaminoborane as liquid and/or solid spent-fuel, consistent with previous reports. Density Functional Theory (DFT) calculations suggested that hydrogen bonding interactions between AB and a polyetheral promoter initially played an important role in increasing the reactivity of B-H bonds of AB by transferring electron density from oxygen atoms of the promoter into B-H bonds of AB. These partially activated, hydridic B-H bonds were proposed to help promote the formation of diammoniate of diborane (DADB), which is considered as a reactive intermediate, eventually enhancing the rate of H2-release from AB. In addition, our in situ solid state (11)B magic angle spinning (MAS) NMR measurements further confirmed that the rate of DADB formation from AB with a small quantity of T4EGDE was found to be much faster than that of pristine AB even at 50 °C. This metal-free method for H2-release from AB with an added, small quantity of polyethers would be helpful to develop feasible hydrogen storage systems for long-term fuel cell applications.
Fuel Cell Research Center, Korea Institute of Science and Technology, 39-1 Hawolgok-dong, Sungbuk-gu, Seoul 136-791, Republic of Korea. cwyoon@kist.re.kr.
Yongmin
Y
Kim
Hyunjae
H
Baek
Jin Hee
JH
Lee
Shinyoung
S
Yeo
Kibum
K
Kim
Son-Jong
SJ
Hwang
Bit
B
Eun
Suk Woo
SW
Nam
Tae-Hoon
TH
Lim
Chang Won
CW
Yoon