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Title: The Effects of Chemical Additives on the Induction Phase in Solid-State Thermal Decomposition of Ammonia Borane

Abstract

The solid-state decomposition of ammonia borane (AB) alone and in the presence of chemical additives was investigated by a series of experimental methods to develop an approach for reducing the induction period for hydrogen release. Gas chromatography techniques were used to measure the yield of hydrogen as a function of time under isothermal conditions between 70 and 90 °C, and the polyaminoborane (PAB) products produced from hydrogen loss from AB show significant cross linking by 11B NMR spectroscopy. Raman microscopy was used to follow the transformation of crystalline AB to amorphous AB with the subsequent formation of the diammoniate of diborane (DADB). A gas burette was used to monitor the time-dependent release of hydrogen from AB in the presence of chemical additives. The combination of these approaches provides insight into the mechanism of hydrogen release from solid AB. The release of molecular hydrogen is described by a process involving sequential induction (disruption of dihydrogen bonds), nucleation (formation of DADB), and growth (hydrogen release through dehydrocoupling). Addition of DADB or ammonium chloride to neat AB significantly reduces the induction time for hydrogen release. The authors wish to acknowledge support from the U.S. Department of Energy’s Office of Energy Efficiency and Renewablemore » Energy. This work was performed as part of the Center of Excellence in Chemical Hydrogen Storage and in collaboration with the International Partnership for the Hydrogen Economy. Pacific Northwest National Laboratory is operated for the U.S. Department of Energy by Battelle.« less

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
952401
Report Number(s):
PNNL-SA-60433
Journal ID: ISSN 0897-4756; CMATEX; EB4202000; TRN: US200913%%553
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials, 20(16):5332-5336
Additional Journal Information:
Journal Volume: 20; Journal Issue: 16; Journal ID: ISSN 0897-4756
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; ADDITIVES; AMMONIA; AMMONIUM CHLORIDES; BORANES; CROSS-LINKING; ENERGY EFFICIENCY; GAS CHROMATOGRAPHY; HYDROGEN; HYDROGEN STORAGE; INDUCTION; MICROSCOPY; MONITORS; NUCLEATION; PYROLYSIS; SPECTROSCOPY; TRANSFORMATIONS; ammonia borane; hydrogen economy; hydrogen release; HYDROGEN STORAGE MATERIAL; DEHYDROGENATION; RELEASE; DIAMMONIATE; DIBORANE; H3NBH3; DIMER; ION

Citation Formats

Heldebrant, David J, Karkamkar, Abhijeet J, Hess, Nancy J, Bowden, Mark E, Rassat, Scot D, Zheng, Feng, Rappe, Kenneth G, and Autrey, Thomas. The Effects of Chemical Additives on the Induction Phase in Solid-State Thermal Decomposition of Ammonia Borane. United States: N. p., 2008. Web. doi:10.1021/cm801253u.
Heldebrant, David J, Karkamkar, Abhijeet J, Hess, Nancy J, Bowden, Mark E, Rassat, Scot D, Zheng, Feng, Rappe, Kenneth G, & Autrey, Thomas. The Effects of Chemical Additives on the Induction Phase in Solid-State Thermal Decomposition of Ammonia Borane. United States. https://doi.org/10.1021/cm801253u
Heldebrant, David J, Karkamkar, Abhijeet J, Hess, Nancy J, Bowden, Mark E, Rassat, Scot D, Zheng, Feng, Rappe, Kenneth G, and Autrey, Thomas. Tue . "The Effects of Chemical Additives on the Induction Phase in Solid-State Thermal Decomposition of Ammonia Borane". United States. https://doi.org/10.1021/cm801253u.
@article{osti_952401,
title = {The Effects of Chemical Additives on the Induction Phase in Solid-State Thermal Decomposition of Ammonia Borane},
author = {Heldebrant, David J and Karkamkar, Abhijeet J and Hess, Nancy J and Bowden, Mark E and Rassat, Scot D and Zheng, Feng and Rappe, Kenneth G and Autrey, Thomas},
abstractNote = {The solid-state decomposition of ammonia borane (AB) alone and in the presence of chemical additives was investigated by a series of experimental methods to develop an approach for reducing the induction period for hydrogen release. Gas chromatography techniques were used to measure the yield of hydrogen as a function of time under isothermal conditions between 70 and 90 °C, and the polyaminoborane (PAB) products produced from hydrogen loss from AB show significant cross linking by 11B NMR spectroscopy. Raman microscopy was used to follow the transformation of crystalline AB to amorphous AB with the subsequent formation of the diammoniate of diborane (DADB). A gas burette was used to monitor the time-dependent release of hydrogen from AB in the presence of chemical additives. The combination of these approaches provides insight into the mechanism of hydrogen release from solid AB. The release of molecular hydrogen is described by a process involving sequential induction (disruption of dihydrogen bonds), nucleation (formation of DADB), and growth (hydrogen release through dehydrocoupling). Addition of DADB or ammonium chloride to neat AB significantly reduces the induction time for hydrogen release. The authors wish to acknowledge support from the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy. This work was performed as part of the Center of Excellence in Chemical Hydrogen Storage and in collaboration with the International Partnership for the Hydrogen Economy. Pacific Northwest National Laboratory is operated for the U.S. Department of Energy by Battelle.},
doi = {10.1021/cm801253u},
url = {https://www.osti.gov/biblio/952401}, journal = {Chemistry of Materials, 20(16):5332-5336},
issn = {0897-4756},
number = 16,
volume = 20,
place = {United States},
year = {2008},
month = {8}
}