A Chemical Route to Activation of Open Metal Sites in the Copper-Based Metal–Organic Framework Materials HKUST-1 and Cu-MOF-2

Abstract

Open coordination sites (OCSs) in metal-organic frameworks (MOFs) often function as key factors in the potential applications of MOFs, such as gas separation, gas sorption, and catalysis. For these applications, the activation process to remove the solvent molecules coordinated at the OCSs is an essential step that must be performed prior to use of the MOFs. To date, the thermal method performed by applying heat and vacuum has been the only method for such activation. In this report, we demonstrate that methylene chloride (MC) itself can perform the activation role: this process can serve as an alternative "chemical route" for the activation that does not require applying heat. To the best of our knowledge, no previous study has demonstrated this function of MC, although MC has been popularly used in the pretreatment step prior to the thermal activation process. On the basis of a Raman study, we propose a plausible mechanism for the chemical activation, in which the function of MC is possibly due to its coordination with the Cu(2+) center and subsequent spontaneous decoordination. Using HKUST-1 film, we further demonstrate that this chemical activation route is highly suitable for activating large-area MOF films.

Effect of hydrophilic Cu3(BTC)2 additives on the performance of PVDF membranes for water flux improvement

“…All samples showed good crystallinity. Both XRD patterns are in good agreement with the single-crystal data of Cu 3 (BTC) 2 reported by Kim et al [18], confirming the phase structure of Cu 3 (BTC) 2 . It was also observed that the intensity of the acid-MOF sample decreased due to the surface modification of the Cu 3 (BTC) 2 crystals.…”

“…The main peaks observed in the survey scan are C1s, O1s, and Cu 2p 3/2 peaks centered at 284.5, 531.1, and 934.14 eV, respectively [18][19][20][21]. After acidification of the MOF sample, the Cu 2p 3/2 signature showed different characteristics.…”

Synthesis and characterization of mesoporous Cu-MOF for laccase immobilization

“…They are difficult to synthesize, however, and are unstable in the aqueous phase. For example, HKUST‐1 (a microporous MOF material with copper as the central ion) that is synthesized by BTC (1,3,5‐benzenetricarboxylic acid) and copper nitrate, will partially collapse if immersed in water for 24 h …”

Thermal Activation of CuBTC MOF for CO Oxidation: The Effect of Activation Atmosphere

“…Various activation methods have been developed, including thermal activation [37][38][39], solvent exchange [40][41][42], freeze-drying [43,44], supercritical CO 2 exchange [45], and chemical treatment [46,47]. Among these, thermal activation is most commonly used for its simplicity and efficiency.…”