Role of Hydrogen Bonding on Transport of Coadsorbed Gases in Metal–Organic Frameworks Materials

Abstract

Coadsorption of multicomponents in metal-organic framework (MOF) materials can lead to a number of cooperative effects, such as modification of adsorption sites or during transport. In this work, we explore the incorporation of NH and HO into MOFs preloaded with small molecules such as CO, CO, and SO. We find that NH (or HO) first displaces a certain amount of preadsorbed molecules in the outer portion of MOF crystallites, and then substantially hinders diffusion. Combining in situ spectroscopy with first-principles calculations, we show that hydrogen bonding between NH (or HO) is responsible for an increase of a factor of 7 and 8 in diffusion barrier of CO and CO through the MOF channels. Understanding such cooperative effects is important for designing new strategies to enhance adsorption in nanoporous materials.

Metal–Organic Frameworks Encapsulating Active Nanoparticles as Emerging Composites for Catalysis: Recent Progress and Perspectives

“…Second, the organic linkers might influence the bandgap energy of MOFs. For examples, when the organic linkers in isoreticular MOFs (IRMOFs) are changed from terephthalic acid to 1,4‐naphthalene dicarboxylic acid and 2,6‐naphthalene dicarboxylic acid, respectively, the corresponding bandgap energy is changed from ≈4.0 to ≈3.8 and ≈3.3 eV . As for UiO‐66(Zr), when benzene‐1,4‐dicarboxylic acid coordinated with Zr 6 O 4 (OH) 4 is functionalized by different functional groups including ‐Br, NO 2 , and NH 2 , the main absorption edge is changed from 320 to 360, 400, and 450 nm in sequence .…”

Influence of Pore Size on Carbon Dioxide Diffusion in Two Isoreticular Metal–Organic Frameworks

“…Future efforts would also benefit from analysis of diffusion under mixed-gas conditions that are more relevant to real-world applications. [41][42][43] Insights from studies of this type and related foregoing work will ultimately assist in the design of improved adsorbents and membranes for gas separations.…”

Mechanistic studies on the conversion of NO gas on urea-iron and copper metal organic frameworks at low temperature conditions: in situ infrared spectroscopy and Monte Carlo investigations

“…2269 cm -1 , and v (CO2(g)): 2350 cm -1 . [51][52][53] In the case of Cu-BTC, an extra band was observed D r a f t corresponding to v (NO2(g)): 1614 cm -1 . 54,55 This may be attributed to the oxidizing ability of Cu for NO(g) in Cu-BTC, which is responsible for the presence of NO 2 species in the gas phase spectra.…”