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Uptakes of 9.2 mmol g−1 (40.5 wt %) for CO2 at 273 K/0.1 MPa and 15.23 mmol g−1 (3.07 wt %) for H2 at 77 K/0.1 MPa are among the highest reported for metal–organic frameworks (MOFs) and are found for a novel, highly microporous copper‐based MOF (see picture; Cu turquoise, O red, N blue). Thermal analyses show a stability of the flexible framework up to 250 °C.
Metal–organic frameworks (MOFs) as highly porous materials have gained increasing interest because of their distinct adsorption properties.1–3 They exhibit a high potential for applications in gas separation and storage,4 as sensors5 as well as in heterogeneous catalysis.6 In the last few years, the H2 storage capacity of MOFs has been considerably increased. Mesoporous MOFs show high adsorption capacities for CH4, CO2, and H2 at high pressures.2, 3, 7–10 To increase the uptake of H2 and CO2 by physisorption at ambient pressure, adsorbents with small micropores as well as high specific surface areas and micropore volumes are required.11, 12 Such microporous materials seem to be more appropriate for gas‐mixture separation by physisorption than mesoporous materials. For gas separation in MOFs the interactions between the fluid adsorptive and “open metal sites” (coordinatively unsaturated binding sites) or the ligands are regarded as important.13 Industrial processes, such as natural‐gas purification or biogas upgrading, can be improved with those materials during a vapor‐pressure swing adsorption cycle (VPSA cycle) or a temperature swing adsorption cycle (TSA cycle).14 The microporous MOF series CPO‐27‐M (M=Mg, Co, Ni, Zn), for example, shows very high CO2 uptakes at low pressures (<0.1 MPa).15, 16 Concerning H2 adsorption, the microporous MOF PCN‐12 offers with 3.05 wt % the highest uptake at ambient pressure and 77 K reported to date.17
Herein, we present a novel microporous copper‐based MOF equation image[Cu(Me‐4py‐trz‐ia)] (1; Me‐4py‐trz‐ia2−=5‐(3‐methyl‐5‐(pyridin‐4‐yl)‐4H‐1,2,4‐triazol‐4‐yl)isophthalate) with extraordinarily high CO2 and H2 uptakes at ambient pressure, the H2 uptake being similar to that in PCN‐12. The ligand Me‐4py‐trz‐ia2−, which can be obtained from cheap starting materials by a three‐step synthesis in good yield, combines carboxylate, triazole, and pyridine functions and is adopted from a recently presented series of linkers,18 for which up to now only a few coordination polymers are known.
Synthesis and crystal structure of a novel copper-based MOF material are presented. The tetragonal crystal structure of [ ∞ 3 ( Cu 4 ( μ 4 -O ) ( μ 2 -OH ) 2 ( Me 2 trz p ba ) 4 ] possesses a calculated solvent-accessible pore volume of 57%. Besides the preparation of single crystals, synthesis routes to microcrystalline materials are reported. While PXRD measurements ensure the phase purity of the as-synthesized material, TD-PXRD measurements and coupled DTA–TG–MS analysis confirm the stability of the network up to 230 °C. The pore volume of the microcrystalline material determined by nitrogen adsorption at 77 K depends on the synthetic conditions applied. After synthesis in DMF/H2O/MeOH the pores are blocked for nitrogen, whereas they are accessible for nitrogen after synthesis in H2O/EtOH and subsequent MeOH Soxhleth extraction. The corresponding experimental pore volume was determined by nitrogen adsorption to be V Pore = 0.58 cm 3 g - 1 . In order to characterize the new material and to show its adsorption potential, comprehensive adsorption studies with different adsorptives such as nitrogen, argon, carbon dioxide, methanol and methane at different temperatures were carried out. Unusual adsorption–desorption isotherms with one or two hysteresis loops are found – a remarkable feature of the new flexible MOF material.
Crystal structures of two metal–organic frameworks (MFU‐1 and MFU‐2) are presented, both of which contain redox‐active CoII centres coordinated by linear 1,4‐bis[(3,5‐dimethyl)pyrazol‐4‐yl] ligands. In contrast to many MOFs reported previously, these compounds show excellent stability against hydrolytic decomposition. Catalytic turnover is achieved in oxidation reactions by employing tert‐butyl hydroperoxide and the solid catalysts are easily recovered from the reaction mixture. Whereas heterogeneous catalysis is unambiguously demonstrated for MFU‐1, MFU‐2 shows catalytic activity due to slow metal leaching, emphasising the need for a deeper understanding of structure–reactivity relationships in the future design of redox‐active metal–organic frameworks. Mechanistic details for oxidation reactions employing tert‐butyl hydroperoxide are studied by UV/Vis and IR spectroscopy and XRPD measurements. The catalytic process accompanying changes of redox states and structural changes were investigated by means of cobalt K‐edge X‐ray absorption spectroscopy. To probe the putative binding modes of molecular oxygen, the isosteric heats of adsorption of O2 were determined and compared with models from DFT calculations. The stabilities of the frameworks in an oxygen atmosphere as a reactive gas were examined by temperature‐programmed oxidation (TPO). Solution impregnation of MFU‐1 with a co‐catalyst (N‐hydroxyphthalimide) led to NHPI@MFU‐1, which oxidised a range of organic substrates under ambient conditions by employing molecular oxygen from air. The catalytic reaction involved a biomimetic reaction cascade based on free radicals. The concept of an entatic state of the cobalt centres is proposed and its relevance for sustained catalytic activity is briefly discussed.