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Title: Clarifying the dehydrogenation pathway of catalysed Li4(NH2)3BH4-LiH composite

Abstract

The effect of different metal oxides (Co3O4 and NiO) on the dehydrogenation reactions pathways of the Li4(NH2)3BH4-LiH composite was investigated. The additives were reduced to metallic species i.e. Co and Ni which act as catalysts by breaking the B-H bonds in the Li-B-N-H compounds. The onset desorption temperature was lowered 32 °C for the Ni-catalysed sample, which desorbed 8.8 wt% hydrogen below 275°C. It was demonstrated that the decomposition of the doped composite followed a mechanism via LiNH2 and Li3BN2 formation as the end product with a strong reduction of NH3 emission. The sample could be partially re-hydrogenated (~1.5 wt%) due to the lithium imide/amide transformation. To understand the LiH role, the Li4(NH2)3BH4-LiH-NiO and the Li4(NH2)3BH4-NiO composites were compared. The absence of LiH as a reactive forced the system to follow another path, which involved the formation of an intermediate phase of composition Li3BN2H2 at the early stages of dehydrogenation and the end desorption products LiNH2 and monoclinic Li3BN2. We showed evidence for the interaction between NiO and LiNH2 during heating and we propose that the presence of Li facilitates a NHx-rich environment and the Ni catalyst mediates the electron transfer to promote NHx coupling.

Authors:
 [1]; ORCiD logo [2];  [3];  [4]
  1. Consejo Nacional de Investigaciones Científicas y Técnicas, CONICET
  2. BATTELLE (PACIFIC NW LAB)
  3. Consejo Nacional de Investigaciones Cientificas y Technicas, Instituto Balseiro, CNEA
  4. Consejo Nacional de Investigaciones Cientificas y Technicas (CONICET), Instituto Balseiro, CNEA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1510435
Report Number(s):
PNNL-SA-129333
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 19; Journal Issue: 47
Country of Publication:
United States
Language:
English
Subject:
hydrogen storage materials, Lithium borohydride

Citation Formats

Amica, G, Ronnebro, Ewa C., Larochette, Pierre, and Gennari, Fabiana. Clarifying the dehydrogenation pathway of catalysed Li4(NH2)3BH4-LiH composite. United States: N. p., 2017. Web. doi:10.1039/C7CP04848C.
Amica, G, Ronnebro, Ewa C., Larochette, Pierre, & Gennari, Fabiana. Clarifying the dehydrogenation pathway of catalysed Li4(NH2)3BH4-LiH composite. United States. doi:10.1039/C7CP04848C.
Amica, G, Ronnebro, Ewa C., Larochette, Pierre, and Gennari, Fabiana. Thu . "Clarifying the dehydrogenation pathway of catalysed Li4(NH2)3BH4-LiH composite". United States. doi:10.1039/C7CP04848C.
@article{osti_1510435,
title = {Clarifying the dehydrogenation pathway of catalysed Li4(NH2)3BH4-LiH composite},
author = {Amica, G and Ronnebro, Ewa C. and Larochette, Pierre and Gennari, Fabiana},
abstractNote = {The effect of different metal oxides (Co3O4 and NiO) on the dehydrogenation reactions pathways of the Li4(NH2)3BH4-LiH composite was investigated. The additives were reduced to metallic species i.e. Co and Ni which act as catalysts by breaking the B-H bonds in the Li-B-N-H compounds. The onset desorption temperature was lowered 32 °C for the Ni-catalysed sample, which desorbed 8.8 wt% hydrogen below 275°C. It was demonstrated that the decomposition of the doped composite followed a mechanism via LiNH2 and Li3BN2 formation as the end product with a strong reduction of NH3 emission. The sample could be partially re-hydrogenated (~1.5 wt%) due to the lithium imide/amide transformation. To understand the LiH role, the Li4(NH2)3BH4-LiH-NiO and the Li4(NH2)3BH4-NiO composites were compared. The absence of LiH as a reactive forced the system to follow another path, which involved the formation of an intermediate phase of composition Li3BN2H2 at the early stages of dehydrogenation and the end desorption products LiNH2 and monoclinic Li3BN2. We showed evidence for the interaction between NiO and LiNH2 during heating and we propose that the presence of Li facilitates a NHx-rich environment and the Ni catalyst mediates the electron transfer to promote NHx coupling.},
doi = {10.1039/C7CP04848C},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 47,
volume = 19,
place = {United States},
year = {2017},
month = {12}
}

Works referenced in this record:

Hydrogen Release from Mixtures of Lithium Borohydride and Lithium Amide:  A Phase Diagram Study
journal, March 2006

  • Meisner, Gregory P.; Scullin, Matthew L.; Balogh, Michael P.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 9
  • DOI: 10.1021/jp056019b

Effective thermodynamic alteration to Mg(NH 2 ) 2 –LiH system: achieving near ambient-temperature hydrogen storage
journal, January 2014

  • Cao, Hujun; Wu, Guotao; Zhang, Yao
  • J. Mater. Chem. A, Vol. 2, Issue 38
  • DOI: 10.1039/C4TA03505D

Impact of Stoichiometry on the Hydrogen Storage Properties of LiNH 2 −LiBH 4 −MgH 2 Ternary Composites
journal, January 2009

  • Sudik, Andrea; Yang, Jun; Siegel, Donald J.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 5
  • DOI: 10.1021/jp807270y

Functions of LiBH4 in the hydrogen sorption reactions of the 2LiH–Mg(NH2)2 system
journal, January 2010

  • Hu, Jianjiang; Weidner, Eveline; Hoelzel, Markus
  • Dalton Transactions, Vol. 39, Issue 38
  • DOI: 10.1039/c0dt00468e

Improved hydrogen storage kinetics of the Li–Mg–N–H system by addition of Mg(BH 4 ) 2
journal, January 2013

  • Pan, Hongge; Shi, Songbo; Liu, Yongfeng
  • Dalton Trans., Vol. 42, Issue 11
  • DOI: 10.1039/C2DT32266H

LiBH4 a new hydrogen storage material
journal, May 2003


Improving Effects of LiH and Co-Catalyst on the Dehydrogenation of Li 4 BN 3 H 10
journal, April 2011

  • Zheng, Xueli; Xiong, Zhitao; Lim, Yonghao
  • The Journal of Physical Chemistry C, Vol. 115, Issue 17
  • DOI: 10.1021/jp2007182

Improved hydrogen release from LiB0.33N0.67H2.67 with metal additives: Ni, Fe, and Zn
journal, May 2007

  • Pinkerton, Frederick E.; Meyer, Martin S.; Meisner, Gregory P.
  • Journal of Alloys and Compounds, Vol. 433, Issue 1-2
  • DOI: 10.1016/j.jallcom.2006.06.108

Nickel- and cobalt-based catalysts for hydrogen generation by hydrolysis of borohydride
journal, May 2006


Ultrafast Reaction between LiH and NH 3 during H 2 Storage in Li 3 N
journal, November 2003

  • Hu, Yun Hang; Ruckenstein, Eli
  • The Journal of Physical Chemistry A, Vol. 107, Issue 46
  • DOI: 10.1021/jp036257b

Surface and bulk reactions in borohydrides and amides
journal, January 2012

  • Borgschulte, Andreas; Jones, Martin O.; Callini, Elsa
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee02975h

A Self-Catalyzing Hydrogen-Storage Material
journal, January 2008

  • Yang, Jun; Sudik, Andrea; Siegel, Donald J.
  • Angewandte Chemie International Edition, Vol. 47, Issue 5
  • DOI: 10.1002/anie.200703756

Hydrogen Desorption Exceeding Ten Weight Percent from the New Quaternary Hydride Li 3 BN 2 H 8
journal, January 2005

  • Pinkerton, Frederick E.; Meisner, Gregory P.; Meyer, Martin S.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 1
  • DOI: 10.1021/jp0455475

Investigation on the Properties of the Mixture Consisting of Mg(NH 2 ) 2 , LiH, and LiBH 4 as a Hydrogen Storage Material
journal, November 2008

  • Hu, Jianjiang; Fichtner, Maximilian; Chen, Ping
  • Chemistry of Materials, Vol. 20, Issue 22
  • DOI: 10.1021/cm802129b

Improved Dehydrogenation and Rehydrogenation Properties of LiBH<sub>4</sub> by Nanosized Ni Addition
journal, January 2014


Towards a viable hydrogen storage system for transportation application
journal, December 2005


Hydrogen Desorption Behavior of Nickel-Chloride-Catalyzed Stoichiometric Li 4 BN 3 H 10
journal, May 2009

  • Pinkerton, F. E.; Meyer, M. S.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 25
  • DOI: 10.1021/jp810208k

Cobalt-catalyzed hydrogen desorption from the LiNH2–LiBH4 system
journal, January 2008

  • Tang, Wan Si; Wu, Guotao; Liu, Tao
  • Dalton Transactions, Issue 18
  • DOI: 10.1039/b719420j

Controlling the Decomposition Pathway of LiBH 4 via Confinement in Highly Ordered Nanoporous Carbon
journal, July 2010

  • Liu, Xiangfeng; Peaslee, David; Jost, C. Z.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 33
  • DOI: 10.1021/jp1055045

Releasing 17.8 wt% H2 from lithium borohydride ammoniate
journal, January 2011

  • Zheng, Xueli; Wu, Guotao; Li, Wen
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c1ee01480c

Microwave Spectrum, Conformational Composition, and Dipole Moment of (Fluoromethyl)cyclopropane (C 3 H 5 CH 2 F)
journal, March 2014

  • Samdal, Svein; Møllendal, Harald; Guillemin, Jean-Claude
  • The Journal of Physical Chemistry A, Vol. 118, Issue 12
  • DOI: 10.1021/jp500985a

Electronic promoter or reacting species? The role of LiNH 2 on Ru in catalyzing NH 3 decomposition
journal, January 2015

  • Guo, Jianping; Chen, Zheng; Wu, Anan
  • Chemical Communications, Vol. 51, Issue 82
  • DOI: 10.1039/C5CC04645A

Superior destabilization effects of LiBH 4 with the addition of nano-sized nickel ferrite NiFe 2 O 4
journal, January 2015


Synthesis, properties and crystal structures of α-Ca3(BN2)2 and Ca9+x(BN2, CBN)6—two compounds with BN23− and CBN4− anions
journal, January 1998

  • Wörle, Michael; Meyer zu Altenschildesche, Holger; Nesper, Reinhard
  • Journal of Alloys and Compounds, Vol. 264, Issue 1-2
  • DOI: 10.1016/S0925-8388(97)00148-5

Determination of the Phase Behavior of (LiNH 2 ) c (LiBH 4 ) 1− c Quaternary Hydrides through in Situ X-ray Diffraction
journal, September 2009

  • Singer, Jonathan P.; Meyer, Martin S.; Speer, Richard M.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 43
  • DOI: 10.1021/jp905970h

Size effects on the hydrogen storage properties of nanoscaffolded Li 3 BN 2 H 8
journal, April 2009


Nanosized Co- and Ni-Catalyzed Ammonia Borane for Hydrogen Storage
journal, June 2009

  • He, Teng; Xiong, Zhitao; Wu, Guotao
  • Chemistry of Materials, Vol. 21, Issue 11
  • DOI: 10.1021/cm900672h

Raman spectroscopic observation of dehydrogenation in ball-milled LiNH2–LiBH4–MgH2 nanoparticles
journal, June 2010

  • Hattrick-Simpers, Jason R.; Maslar, James E.; Niemann, Michael U.
  • International Journal of Hydrogen Energy, Vol. 35, Issue 12
  • DOI: 10.1016/j.ijhydene.2010.02.101

The role of Ni in increasing the reversibility of the hydrogen release from nanoconfined LiBH4
journal, January 2011

  • Ngene, Peter; Verkuijlen, Margriet H. W.; Zheng, Qiang
  • Faraday Discussions, Vol. 151
  • DOI: 10.1039/c0fd00028k

Role of Co3O4 in improving the hydrogen storage properties of a LiBH4–2LiNH2 composite
journal, January 2014

  • Zhang, Yu; Liu, Yongfeng; Pang, Yuepeng
  • Journal of Materials Chemistry A, Vol. 2, Issue 29
  • DOI: 10.1039/c4ta01422g

Remarkable decrease in dehydrogenation temperature of Li–B–N–H hydrogen storage system with CoO additive
journal, October 2013


Mechanistic understanding of CoO-catalyzed hydrogen desorption from a LiBH 4 ·NH 3 –3LiH system
journal, January 2015

  • Zhang, Yi; Liu, Yongfeng; Zhang, Xin
  • Dalton Transactions, Vol. 44, Issue 32
  • DOI: 10.1039/C5DT02148K

Improvement of Hydrogen Storage Properties of the Li–Mg–N–H System by Addition of LiBH 4
journal, July 2008

  • Hu, Jianjiang; Liu, Yongfeng; Wu, Guotao
  • Chemistry of Materials, Vol. 20, Issue 13
  • DOI: 10.1021/cm800584x

Effective participation of Li 4 (NH 2 ) 3 BH 4 in the dehydrogenation pathway of the Mg(NH 2 ) 2 –2LiH composite
journal, January 2016

  • Amica, G.; Cova, F.; Arneodo Larochette, P.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 27
  • DOI: 10.1039/C6CP02854C

Solid-state NMR and thermodynamic investigations on LiBH4LiNH2 system
journal, August 2016

  • Wolczyk, Anna; Pinatel, Eugenio R.; Chierotti, Michele R.
  • International Journal of Hydrogen Energy, Vol. 41, Issue 32
  • DOI: 10.1016/j.ijhydene.2016.03.040

Lithium Imide Synergy with 3d Transition-Metal Nitrides Leading to Unprecedented Catalytic Activities for Ammonia Decomposition
journal, January 2015

  • Guo, Jianping; Wang, Peikun; Wu, Guotao
  • Angewandte Chemie International Edition, Vol. 54, Issue 10
  • DOI: 10.1002/anie.201410773