CuSiF_6(4,4'-bipyridine)_2, a Crystalline Complex with Excellent Adsorptivity for Thiophenic Sulfur Compounds in Model Oil

摘要

CuSiF6(4,4'-bip-yridine)(2) (SIFSIX-1-Cu) is a crystalline complex of CuSiF6 and 4,4'-bipyridine with rich microporosity, high specific area (similar to 1100 m(2).g(-1)), and negligible hydroscopicity. Furthermore, this complex can be synthesized and dried under much milder conditions compared with conventional MOFs. In this paper, three complexes, SIFSIX-1-Cu(1), SIFSIX-1-Cu(2), and SIFSIX-1-Cu(3), were prepared using Cu(BF4)(2), Cu(NO3)(2), and CuSO4, respectively, as the copper sources, and their structure was characterized by SEM, XPS, XRD, and N-2-adsorption desorption measurements. The adsorptivity of these compounds for dibenzothiophene (DBT) in model oil follows the order of SIFSIX-1-Cu(1) SIFSIX-1-Cu(2) SIFSIX-1-Cu(3), which is consistent with the order of their crystallinity and specific areas. The adsorption amount of SIFSIX-1-Cu(1) is 49.5 mg-S.g(-1) for DBT model oil at an equilibrium sulfur concentration of 700 ppm and 303.15 K, and follows the order of DBT benzothiophene (BT) 3-methylthiophene (3-MT) for other sulfur compounds. The adsorptive desulfurization performance of SIFSIX-1-Cu is one of competitive sorbents among MOFs. The used sorbent can be regenerated easily by methanol washing and can be reused with an approximately 11% loss of adsorption capacity after five cycles. This study reveals the potential application of microporous crystal complexes for fuel desulfurization.