Homogeneous and Heterogeneous Catalysis at Work in Lightweight Inorganic Hydride Dehydrogenation (Chemical Hydrogen Storage)

A special issue of Hydrogen (ISSN 2673-4141).

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 4925

Special Issue Editor

National Research Council, Institute of Chemistry of Organometallic Compounds (ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino, Firenze, Italy
Interests: B/N-based lightweight inorganic hydrides; hydrogen storage; metal-organic frameworks; CO2 storage and utilization
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Special Issue Information

Dear Colleagues,

The quest for new solid-state materials for hydrogen storage is continuously growing. Hydrogen is the lightest element in the Universe, and H2 has the largest gravimetric energy density of all chemical substances. Unfortunately, H2 has a very low density both as a gas and as a liquid. Therefore, its volumetric energy density is very low, which is a major drawback for the utilization of H2 as a gas, in particular for electronics (mobile hydrogen fuel cell technology) and in the automotive world (hydrogen reservoirs to be used on fuel-cell-powered cars). Hydrogen could be chemically stored into stable and non-toxic compounds that easily release it on demand, under mild temperature and pressure conditions. In addition, an easy regeneration of the “spent fuel” would be desirable. The optimal material for this task has not been found yet, but a range of (old and) new lightweight solid hydrides with fascinating properties have been (re)discovered and examined from a different perspective in recent years. Lightweight hydrides containing metals from Groups 1/2 (Li, Na, Mg, Ca) and elements from Groups 13/15 (B, Al, N) of the Periodic Table are of particular interest in this regard, as they offer an appropriate balance of volumetric (rv) and gravimetric (rm) hydrogen densities. Among them are ammonia borane (NH3BH3 (AB); rm = 19.6 wt.% H), amine boranes (RNH2BH3, R = aliphatic ring or chain), hydrazine (H2N-NH2, rm = 12.5 wt.% H), hydrazine borane (N2H4∙BH3 (HB); rm = 15.4 wt.% H), hydrazine bis(borane) (N2H4∙2BH3 (HBB); rm = 16.7 wt.% H), borohydrides (M(BH4); M = Li, Na) and aluminum hydrides (alanates) (M(AlH4); M = Li, Na). Up to four equivalents of high-purity (carbon-free) hydrogen can be extracted from these molecules under relatively mild temperature conditions through the employ of a metal-containing homogeneous or heterogeneous catalyst. The former is an organometallic/coordination compound containing assorted metal ions from all over the Periodic Table, while the latter consists of supported monometallic, multimetallic or core-shell M(0) nanoparticles (NPs). The metallic NPs are normally deposited on the support through a sequential impregnation/reduction protocol. In all cases, the catalyst efficiency is measured and compared in terms of the number of H2 equivalents produced, reaction rate and operative temperature. This Special Issue aims to collect full papers/critical reviews on the topic of catalyzed lightweight inorganic hydride dehydrogenation, possibly covering all the aforementioned contexts. Scientific productions of both experimental and computational nature are welcome.

Dr. Andrea Rossin
Guest Editor

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  • chemical hydrogen storage
  • lightweight inorganic hydrides
  • homogeneous dehydrogenation catalysis
  • heterogeneous dehydrogenation catalysis

Published Papers (1 paper)

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13 pages, 4616 KiB  
Influence of Synthesis Gas Components on Hydrogen Storage Properties of Sodium Aluminum Hexahydride
Hydrogen 2021, 2(1), 147-159; https://doi.org/10.3390/hydrogen2010009 - 26 Feb 2021
Cited by 2 | Viewed by 3273
A systematic study of different ratios of CO, CO2, N2 gas components on the hydrogen storage properties of the Na3AlH6 complex hydride with 4 mol% TiCl3, 8 mol% aluminum and 8 mol% activated carbon is [...] Read more.
A systematic study of different ratios of CO, CO2, N2 gas components on the hydrogen storage properties of the Na3AlH6 complex hydride with 4 mol% TiCl3, 8 mol% aluminum and 8 mol% activated carbon is presented in this paper. The different concentrations of CO and CO2 in H2 and CO, CO2, N2 in H2 mixture were investigated. Both CO and CO2 gas react with the complex hydride forming Al oxy-compounds, NaOH and Na2CO3 that consequently cause serious decline in hydrogen storage capacity. These reactions lead to irreversible damage of complex hydride under the current experimental condition. Thus, after 10 cycles with 0.1 vol % CO + 99.9 vol %H2 and 1 vol % CO + 99 vol %H2, the dehydrogenation storage capacity of the composite material decreased by 17.2% and 57.3%, respectively. In the case of investigation of 10 cycles with 1 vol % CO2 + 99 vol % H2 gas mixture, the capacity degradation was 53.5%. After 2 cycles with 10 vol % CO +90 vol % H2, full degradation was observed, whereas after 6 cycles with 10 vol % CO2 + 90 vol % H2, degradation of 86.8% was measured. While testing with the gas mixture of 1.5 vol % CO + 10 vol % CO2 + 27 vol % H2 + 61.5 vol % N2, the degradation of 94% after 6 cycles was shown. According to these results, it must be concluded that complex aluminum hydrides cannot be used for the absorption of hydrogen from syngas mixtures without thorough purification. Full article
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