Optimal Binding of Acetylene to a Nitro-Decorated Metal–Organic Framework

Abstract

We report the first example of crystallographic observation of acetylene binding to −NO2 groups in a metal–organic framework (MOF). Functionalization of MFM-102 with −NO2 groups on phenyl groups leads to a 15% reduction in BET surface area in MFM-102-NO2. However, this is coupled to a 28% increase in acetylene adsorption to 192 cm3 g–1 at 298 K and 1 bar, comparable to other leading porous materials. Neutron diffraction and inelastic scattering experiments reveal the role of −NO2 groups, in cooperation with open metal sites, in the binding of acetylene in MFM-102-NO2.

Unraveling Structure and Dynamics in Porous Frameworks via Advanced In Situ Characterization Techniques

“…A similar in situ NPD study with C 2 D 2 was conducted by Schröder and co‐workers on the nitro‐functionalized MFM‐102‐NO 2 framework showing increased acetylene capacity . Crystallographic studies proved a counterintuitive binding between electron‐rich C 2 H 2 molecules and electron withdrawing −NO 2 groups in the MOF, MFM‐102‐NO 2 .…”

“…A similar in situ NPD study with C 2 D 2 was conducted by Schröder and co-workers on the nitro-functionalized MFM-102-NO 2 framework showing increased acetylene capacity. [136] Crystallographic studies proved a counterintuitive binding between electron-rich C 2 H 2 molecules and electron withdrawing −NO 2 groups in the MOF, MFM-102-NO 2 . Using the same experimental protocol, oxygen binding to unsaturated metal centers of CPO-27 series was explored by Dietzel and co-workers.…”

Observation of binding of carbon dioxide to nitro-decorated metal–organic frameworks

“…Synthesis, structure and porosity MFM-102, MFM-102-NH 2 , MFM-102-NO 2 and MFM-111 were synthesised according to our previously reported methods, [16][17][18] and the phase purity of all bulk materials was conrmed by powder X-ray diffraction (see ESI † Section 1). All four MOFs are iso-structural and crystallise in the trigonal space group R 3m.…”

“…The detailed synthesis of MFM-102 has been reported previously. 16 1 H NMR and 13 C NMR spectra were measured on a Bruker AV400 or AV500 spectrometer. Highresolution electrospray mass spectra were measured on a Bruker MicroTOF spectrometer with samples dissolved in MeOH, and scanning was conducted in both positive and negative modes.…”

Dynamics & Spectroscopy with Neutrons—Recent Developments & Emerging Opportunities

“…Developments in gas-handling systems have also paved the way to probe gate-opening and related network-breathing phenomena arising from the unique elastic properties of MOFs—see entries in Table 1 and Refs. [ 151 , 266 , 267 , 268 , 269 , 270 , 271 , 272 , 273 , 274 , 275 , 276 , 277 , 278 , 279 , 280 , 281 , 282 , 283 , 284 , 285 , 286 , 287 , 288 , 289 , 290 ].…”