ABSTRACT
Heterometallic cobalt p-tert-butylcalix[6 and 8]arenes have been generated from the in situ reaction of lithium reagents (n-BuLi or t-BuOLi) or NaH with the parent calix[n]arene and subsequent reaction with CoBr2. The reverse route, involving the addition of in situ generated Li[Co(Ot-Bu)3] to p-tert-butylcalix[6 and 8]arene, has also been investigated. X-ray crystallography reveals the formation of complicated products incorporating differing numbers of cobalt and lithium or sodium centers, often with positional disorder, as well as, in some cases, the retention of halide. The electrochemical analysis revealed several oxidation events related to the subsequent oxidation of Co(ii) centers and the reduction of the metal cation at negative potentials. Moreover, the electrochemical activity of the phenol moieties of the parent calix[n]arenes resulted in dimerized products or quinone derivatives, leading to insoluble oligomeric products that deposit and passivate the electrode. Preliminary screening for electrochemical proton reduction revealed good activity for a number of these systems. Results suggest that [Co6Na(NCMe)6(µ-O)(p-tert-butylcalix[6]areneH)2Br]·7MeCN (6·7MeCN) is a promising molecular catalyst for electrochemical proton reduction, with a mass transport coefficient, catalytic charge transfer resistance and current magnitude at the catalytic turnover region that are comparable to those of the reference electrocatalyst (Co(ii)Cl2).
ABSTRACT
Due to their large specific surface areas and porosity, metal-organic frameworks (MOFs) have found many applications in catalysis, gas separation, and gas storage. However, their use as electronic components such as supercapacitors is stunted due to their poor electrical conductivity. We report a remedy for this by combining the MOF structure with polypyrrole (PPy), a well-known conductive polymer. Three MOFs are studied for modification to this end: CPO-27-Ni and CPO-27-Co (M2DOBDC, M = Ni2+, Co2+, DOBDC = 2,5-dihydroxy-1,4-benzenedicarboxylate) and HKUST-1 (Cu3(BTC)2, BTC = 1,3,5 benzenetricarboxylate). The gravimetric capacitance of pure MOFs is boosted several orders of magnitude after reinforcement of PPy (e.g., from 0.679 to 185 F g-1 for HKUST-1 and PPy-HKUST-1, respectively), and is much higher than reported for pure PPy. In total, these PPy-d-MOFs exhibit specific capacitances up to 354 F g-1, retaining 70% of this value even after 2500 cycles. Among them, the highest capacitance is found for PPy-CPO-27-Ni (354 F g-1), followed by PPy-CPO-27-Co (263 F g-1) and PPy-HKUST-1 (185 F g-1). The maximum operating potential for these electrodes is 0.5 V, which is restricted by the contact of MOF with aqueous electrolyte and with extremely low PPy content. As a solution, higher PPy loading and rational adjustment of particle size and porosity of both MOF and PPy are recommended so that the MOF/electrolyte interface is limited, leading to more robust electrode. The work completed here describes a highly promising approach to tackling the electrically insulating nature of MOFs, paving the way for their use in electrochemical energy storage devices.
ABSTRACT
Reaction of differing amounts of vanadyl sulfate with p-tert-butylthiacalix[4]areneH4 and base allows access to the vanadyl-sulfate species [NEt4]4[(VO)4(µ3-OH)4(SO4)4]·½H2O (1), [HNEt3]5[(VO)5(µ3-O)4(SO4)4]·4MeCN (2·4MeCN) and [NEt4]2[(VO)6(O)2(SO4)4(OMe)(OH2)]·MeCN (3·MeCN). Similar use of p-tert-butylsulfonylcalix[4]areneH4, p-tert-butylcalix[8]areneH8 or p-tert-butylhexahomotrioxacalix[3]areneH3 led to the isolation of [HNEt3]2[H2NEt2]2{[VO(OMe)]2p-tert-butylcalix[8-SO2]areneH2} (4), [HNEt3]2[V(O)2p-tert-butylcalix[8]areneH5] (5) and [HNEt3]2[VIV2VV4O11(OMe)8] (6), respectively. Dc magnetic susceptibility measurements were performed on powdered microcrystalline samples of 1-3 in the T = 300-2 K temperature range. Preliminary screening for electrochemical water oxidation revealed some activity for 2 with turnover frequency (TOF) and number (TON) of 2.2 × 10-4 s-1 and 6.44 × 10-6 (mmol O2/mmol cat.), respectively. The compound 3 showed an improved electrochemical activity in the presence of water. This is related to the increased number and the rate of electrons exchanged during oxidation of V4+ species, facilitated by protons generated in the water discharge process.
