Computational Design of Porous Organic Frameworks for High-Capacity Hydrogen Storage by Incorporating Lithium Tetrazolide Moieties

Abstract

We propose to incorporate a lithium tetrazolide group into porous materials for enhancing hydrogen storage capacity. The lithium tetrazolide group is much more stable and polarized than the models made by doping aromatic groups with lithium atoms. More importantly, each of the lithium tetrazolide provides 14 binding sites for hydrogen molecules with modest interaction energies. The advantage of multiple binding sites with modest binding energies is partially demonstrated by constructing a new porous aromatics framework (PAF-4) with the lithium tetrazolide moieties and predicting its hydrogen uptake using firstprinciples GCMC simulations. The predicted hydrogen uptake reaches 4.9 wt % at 233 K and 10 MPa, which exceeds the 2010 DOE target of 4.5 wt %. SECTION Nanoparticles and Nanostructures

Porous aromatic frameworks: Synthesis, structure and functions

“…6) with dia topology and simulated results show very promising hydrogen uptake reaches 4.9 wt% at 233 K and 10 MPa, which exceeds the 2010 DOE target of 4.5 wt%. 83 Jiang et al designed a new PAF by introducing polar organic groups into the biphenyl unit (Fig. 7) and investigated their separating power toward carbon dioxide by using grandcanonical Monte Carlo (GCMC) simulations.…”

Enthalpy–Entropy Correlation for Hydrogen Adsorption on MOFs: Variable‐Temperature FTIR Study of Hydrogen Adsorption on MIL‐100(Cr) and MIL‐101(Cr)

“…Strategies for increasing the gas-solid interaction energy include creation of coordinatively unsaturated (open) metal cation sites in the framework [15][16][17][18] and doping of (functionalized) MOFs with alkali or alkaline-earth metal cations. [19][20][21][22][23] Extensive experimental work, summarized in several recent reviews, [24][25][26][27][28] shows that the adsorption enthalpy of molecular hydrogen on MOFs not having unsaturated metal cations tends to be in the range -4 to -6 kJ mol -1 , which is too small for relevant uptake near ambient temperature. However, when open metal cation centres can be were obtained.…”

Hydrogen storage in porous structures of adamantane-based nitrogen-heterocyclic ring with diamond-like structure

“…The curves converge into a straight line at different values for different materials. It can reflect that additional molecules are distributed in various binding sites . The isosteric heat of low loading amount is higher than that of high loading amount at 77 K because little amount of H 2 molecules can lie at the adsorption sites with stronger interaction.…”

“…Those structures have been used as potential chemical building blocks for new hydrogen storage materials, such as porous aromatic frameworks (PAFs) and adamantane‐based aromatic frameworks (AAFs) . It is also well known that nitrogen‐heterocyclic ring as the linkers are often used in synthesis of porous materials such as MOFs, COFs, PAF‐4 . So, we will use them as the compositions of the simulative porous materials.…”