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Title: Anomalous H2 Desorption Rate of NaAlH4 Confined in Nitrogen-Doped Nanoporous Carbon Frameworks

Journal Article · · Chemistry of Materials
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [3];  [4];  [3];  [3];  [1]
  1. Univ. of Missouri - Saint Louis, Saint Louis, MO (United States)
  2. Washington Univ., St. Louis, MO (United States)
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  4. Washington Univ., St. Louis, MO (United States); ABQMR Inc., Albuquerque, NM (United States)
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Confining NaAlH4 in nanoporous carbon scaffolds is known to alter the sorption kinetics and/or pathways of the characteristic bulk hydride reactions through interaction with the framework at the interface, increased specific surface area of the resulting nanoparticles, decreased hydrogen diffusion distances, and prevention of phase segregation. Although the nanosize effects have been well studied, the influence of the carbon scaffold surface chemistry remains unclear. Here we compare the hydrogen sorption characteristics of NaAlH4 confined by melt infiltration in nitrogen-doped/undoped ordered nanoporous carbon of two different geometries. 23Na and 27Al MAS NMR, N2 sorption, and PXRD verify NaAlH4 was successfully confined and remains intact in the carbon nanopores after infiltration. Both the N-doped/undoped nanoconfined systems demonstrate improved reversibility in relation to the bulk hydride during hydrogen desorption/absorption cycling. Isothermal kinetic measurements indicate a lowering of the activation energy for H2 desorption by as much as 70 kJ/mol in N-doped frameworks, far larger than the reduction in carbon-only frameworks. Most interestingly, this dramatic lowering of the activation energy is accompanied by an unexpected and anomalously low NaAlH4 desorption rate in the N-doped frameworks. This suggests that the framework surface chemistry plays an important role in the desorption process and that the rate limiting step for desorption may be associated with interactions of the hydride and host surface. Our results indicate that functionalization of carbon scaffold surface chemistry with heteroatoms provides a powerful method of altering the characteristic hydrogen sorption properties of confined metal hydride systems. Furthermore, this technique may prove beneficial in the path to a viable metal hydride-based hydrogen storage system.

Research Organization:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1464194
Alternate ID(s):
OSTI ID: 1507405
Report Number(s):
SAND-2018-4114J; SAND2019-3248J; 666285
Journal Information:
Chemistry of Materials, Vol. 30, Issue 9; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 37 works
Citation information provided by
Web of Science

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  • Bhakta, Raghunandan K.; Herberg, Julie L.; Jacobs, Benjamin
  • Journal of the American Chemical Society, Vol. 131, Issue 37, p. 13198-13199 https://doi.org/10.1021/ja904431x
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Cited By (4)

Complex Hydrides for Energy Storage, Conversion, and Utilization journal July 2019
Voltage-Relaxation GITT and Reverse Monte Carlo to Determine Lithium Diffusion and Distribution in TiO 2 and Highly-Ordered Nanoporous Hard Carbons journal January 2018
Alanates, a Comprehensive Review journal September 2019
Tuning LiBH4 for Hydrogen Storage: Destabilization, Additive, and Nanoconfinement Approaches journalarticle January 2019

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