TY - JOUR
T1 - Pyridine-M2+ [M = Mg, Ca]
T2 - A promising organometallic system for potential hydrogen storage: In silico study
AU - Dash, Mrinal Kanti
AU - Jain, Amul
AU - Dhruw, Leena
AU - Giri, Santanab
AU - Guo, Zhanhu
AU - Roymahapatra, Gourisankar
N1 - Funding information: All authors would like to thank the Haldia Institute of Technology, Haldia-721657, WB, India, for supporting resources and computational facilities. M K Dash also thanks the Software for Chemistry & Materials to give scope for evaluating the Amsterdam Modelling Suite. This work is an extension and detailed study of the mini-project done by Amul Jain during his M.Sc. course study.
PY - 2023/8/1
Y1 - 2023/8/1
N2 - Pyridine-M2+ [M = Mg, Ca] hosts have been identified as potent H2 storage material, and this has been explored by a variety of functionals within the density functional theory (DFT) context. Around the linearly connected metal centre, the pyridine-Mg2+ and pyridine-Ca2+ building blocks can adsorb 6 and 7H2 molecules, respectively. The stability of Pyridine-M2+ [M = Mg, Ca] hosts has been proven by chemical hardness, aromaticity, and molecular dynamic simulations. After H2 adsorption, the aromaticity still remains. Adsorption of H2 molecules at a quasi-molecular type is supported by the fact that their average adsorption energy/H2 (Eads/H2) is between 0.22 and 0.72 eV. Pyridine-Mg2+@6H2 and pyridine-Ca2+@7H2 both have very impressive gravimetric wt % values (10.43 and 10.53 respectively). Average delocalization correction energy (ΔECTav) supports the charge transfer type interaction between metal ions and adsorbed H2 molecules. The topological analysis reflects that bonding between metals (Mg & Ca) and trapped H2 molecules are mostly non-covalent types. Gibbs free energy changes (ΔG) [eV] indicate that the molecular hydrogen adsorption process will be spontaneous at 298 K for pyridine-Mg2+@nH2 systems and at or below 205 K for pyridine-Ca2+@nH2 systems and atom centered density matrix propagation (ADMP) study suggests the higher temperature for desorption.
AB - Pyridine-M2+ [M = Mg, Ca] hosts have been identified as potent H2 storage material, and this has been explored by a variety of functionals within the density functional theory (DFT) context. Around the linearly connected metal centre, the pyridine-Mg2+ and pyridine-Ca2+ building blocks can adsorb 6 and 7H2 molecules, respectively. The stability of Pyridine-M2+ [M = Mg, Ca] hosts has been proven by chemical hardness, aromaticity, and molecular dynamic simulations. After H2 adsorption, the aromaticity still remains. Adsorption of H2 molecules at a quasi-molecular type is supported by the fact that their average adsorption energy/H2 (Eads/H2) is between 0.22 and 0.72 eV. Pyridine-Mg2+@6H2 and pyridine-Ca2+@7H2 both have very impressive gravimetric wt % values (10.43 and 10.53 respectively). Average delocalization correction energy (ΔECTav) supports the charge transfer type interaction between metal ions and adsorbed H2 molecules. The topological analysis reflects that bonding between metals (Mg & Ca) and trapped H2 molecules are mostly non-covalent types. Gibbs free energy changes (ΔG) [eV] indicate that the molecular hydrogen adsorption process will be spontaneous at 298 K for pyridine-Mg2+@nH2 systems and at or below 205 K for pyridine-Ca2+@nH2 systems and atom centered density matrix propagation (ADMP) study suggests the higher temperature for desorption.
KW - Average adsorption energy
KW - Binding energy
KW - Gravimetric wt %
KW - Topological analysis
UR - http://www.scopus.com/inward/record.url?scp=85162970867&partnerID=8YFLogxK
U2 - 10.1016/j.jics.2023.101048
DO - 10.1016/j.jics.2023.101048
M3 - Article
AN - SCOPUS:85162970867
SN - 0019-4522
VL - 100
JO - Journal of the Indian Chemical Society
JF - Journal of the Indian Chemical Society
IS - 8
M1 - 101048
ER -