Project Details Critical evaluation of thermodynamic properties of hydrogen storage materials: metal organic frameworks and metal or complex hydrides

Project No.:
Start Date:
01 March 2009
End Date:
31 May 2014


The primary purpose of the project is to investigate the thermodynamics of hydrogen production and storage, as a basis for the development of materials with improved hydrogen storage capability. This will be a systematic study of hydrogen adsorption/absorption by divided/confined materials (frameworks, for example Metal Organic Frameworks, MOFs, such as Li-MOFs), and the study of hydrogen production by (thermal) decomposition of Metal Hydrides (MHs, such as La-Mg-Ni/TiCrV-hydrides, MgH2 ,etc.), and Inorganic Hydrides (Complex Hydrides, such as Li(Na, K, Mg)BH4, Li-N-H, etc.).
The project will consist of 3 major components:
a. Establishing a comprehensive bibliography.
b. Critical evaluation and compilation of the data.
c. Creating an open domain XML-based Web archive so that the results will be freely available.


For the past several decades, hydrogen has been targeted as the utopian fuel for the transportation systems of the future due to its high natural abundance and environmental friendliness. The use of hydrogen within H2/O2 fuel cell systems requires an adequate and readily accessible hydrogen-storage medium. Metal Organic Frameworks (MOFs), Metal Hydrides (MHs) and Inorganic Hydrides (Complex Hydrides) are considered as promising candidates for hydrogen storage. Porous materials, such as MOFs can store considerable quantities of hydrogen at a rather low temperature for their light weight and high surface areas and the ability to physisorb molecular hydrogen. MHs such as LaNi5 hydride have been used for practical application in fuel cells in electrical vehicles. However, none of the present hydrogen storage materials can meet the requirement of the Department of Energy and the International Energy Agency whereby the amount of reversibly adsorbed/desorbed hydrogen exceeds 6.5 wt % and more than 65 g/L. It is very necessary to develop new hydrogen storage materials.

Thermodynamic data play an important role in the initial design and preparation of new hydrogen storage materials. At present, there is no comprehensive database or management system specifically designed for hydrogen storage thermodynamic data.

We propose to meet these needs by conducting a systematic study of new hydrogen storage materials which will involve:
(a) critical evaluation of experimental techniques and measurements of:
i. heat capacities, and derivation of entropy and enthalpy data (e.g., Li-MOFs, etc.)
ii. enthalpy of adsorption/absorption of hydrogen on these materials, or of thermal decomposition
iii. hydrogen storage capacity
(b) assessment of the interaction of hydrogen with these materials
(c) comparisons between theory and experiment
(d) critical evaluation and compilation of the data
(e) establishing a comprehensive bibliography
(f) creation of an open domain XML-based Web archive so that the results will be freely available.
It is also the intention during the period of this project to undertake measurements of properties listed under (a) above. This work will be supported by non-IUPAC bodies. It is expected that the number of
thermodynamic data which are published as a result in peer-reviewed papers in time for inclusion in the present systematic study will be about 15% of the total.


March 2011 update – The Task Group has collected performance data about several hundreds of hydrogen storage materials from published references. Experimental studies on synthesis and hydrogen storage properties of metal organic frameworks, metal hydrides, and complex hydrides have been done. In Sun’s group, they have studied hydrogen storage capacity and thermophysical properties of complex hydrides and metal organic frameworks. The following references relate to this project:

  1. Zhang, J.; Sun, L.; Xu, F.; Li, F.; Zhou, H. Y.; Huang, F. L.; Gabelica, Z.; Schick, C. Hydrogen storage and selective carbon dioxide capture in a new chromium (iii)-based infinite coordination polymer. RSC Advances 2012, 2(7), 2939-2945. [doi:10.1039/C2RA01188C]
  2. Zhang, J.; Sun, L.; Xu, F.; Li, F.; Zhou, H. Y.; Liu, Y. L.; Gabelica, Z.; Schick, C. H2 storage and CO2 capture on a nanoscale metal organic framework with high thermal stability. Chem. Commun. 2012, 48(5), 759-761. [doi:10.1039/C1CC15106A]
  3. Liu, S. S.; Sun, L. X.; Zhang, Y.; Xu, F.; Zhang, J.; Chu, H. L.; Fan, M. Q.; Zhang, T.; Song, X. Y.; Grolier, J. P. Effect of ball milling time on the hydrogen storage properties of TiF3-doped LiAlH4. Int. J. Hydrogen Energy 2009, 34(19), 8079-8085.[doi:10.1016/j.ijhydene.2009.07.090]
  4. Liu, S, Sun, LX, Xu, F, Zhang, J, Jiao, CL, Li, F, Li, ZB, Wang, S, Wang, ZQ, Jiang, X , Zhou, HY , Yang, LN , Schick, C, Nanosized Cu-MOFs induced by graphene oxide and enhanced gas storage capacity, Energy & Environmental Science, 2013,6(3)818-823. [doi:10.1039/C3EE23421E]
  5. Liu, SS; Li, ZB; Jiao, CL; Si, XL; Yang, LN; Zhang, J; Zhou, HY; Huang, FL; Gabelica, Z; Schick, C ; Sun, LX ; Xu, F, Improved reversible hydrogen storage of LiAlH4 by nano-sized TiH2, Int. J. Hydrogen Energy 2013, 38(6), 2770-2777. [doi:10.1016/j.ijhydene.2012.11.042]

Some of the work published was achieved with joint contributions from task group members.

Project completed

last update 5 June 2014