Enhancing H₂ Uptake by “Close‐Packing” Alignment of Open Copper Sites in Metal–Organic Frameworks

Abstract

Open and close: Inspired by close‐packing of spheres, to strengthen the framework–H2 interaction in MOFs (metal‐organic frameworks), a strategy is devised to increase the number of nearest neighboring open metal sites of each H2‐hosting cage, and to align the open metal sites toward the H2 molecules. Two MOF polymorphs were made, one exhibiting a record high hydrogen uptake of 3.0 wt % at 1 bar and 77 K.

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

“…While these are required properties for high gravimetric hydrogen uptake at low temperature, [13,14] a relatively high binding affinity for hydrogen is also needed when hydrogen storage at (or near) ambient temperature is sought. 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.…”

A new mfj-type metal–organic framework constructed from a methoxyl derived V-shaped ligand and its H2, CO2 and CH4 adsorption properties

“…Besides NbO-MOFs, building other types of MOFs from non-linear tetracarboxylic ligands, V-shaped ligands for instance, is another eld of endeavour. [28][29][30][31][32][33] These non-NbO-type MOFs also demonstrated their great potential in hydrogen adsorption and methane storage, as illustrated by PCN-12 (ref. 28) and PCN-14.…”

Effect of Transition Metal Cations on Assembly of Highly Ordered 2D Multiporphyrin Arrays on Liquid and Solid Substrates

“…Первые исследования МОК были направлены на получение ма-териалов с предельно высокими площадью поверхно-сти и объемом пор для хранения водорода и метана. [1][2][3][4] Эти «классические» области использования МОК как микропористых структур были стремительно распро-странены на другие сферы потенциального примене-ния, простирающиеся далеко за пределы сорбционных материалов. Исследование МОК-структур подтвердило перспективы их применения в качестве основы для получения нового класса материалов, обладающих существенными преимуществами в широком ряде об-ластей: хранение, транспортировка и разделение газов, катализ, фотоника, электроника, сенсорика и многие другие.…”