Mixed-Metal Cu-BTC Metal–Organic Frameworks as a Strong Adsorbent for Molecular Hydrogen at Low Temperatures

摘要

The advancement of hydrogen and fuel cell technologies hinges on the development of hydrogen storage methods. Metal–organic frameworks (MOFs) are one of the most favorable materials for hydrogen storage. In this study, we synthesized a series of isostructural mixed-metal metal–organic frameworks (MM-MOFs) of 1,3,5-benzenetricarboxylate (BTC), M-Cu-BTC, where M = Zn~(2+), Ni~(2+), Co~(2+), and Fe~(2+) using the post-synthetic exchange (PSE) method with metal ions. The powder X-ray diffraction patterns of MM-MOFs were similar with those of single-metal Cu-BTC. Scanning electron microscopy indicates the absence of amorphous phases. Inductively coupled plasma mass spectroscopy of the MM-MOFs shows successful metal exchanges using the PSE method. The N_(2) adsorption measurements confirmed the successful synthesis of porous MM-MOFs. The metal exchanged materials Ni-Cu-BTC, Zn-Cu-BTC, Fe-Cu-BTC, and Co-Cu-BTC were studied for hydrogen storage and showed a gravimetric uptake of 1.6, 1.63, 1.63, and 1.12 wt %; respectively. The increase in hydrogen adsorption capacity for the three metal exchanged materials is about 60% relative to that of the parent MOF (Cu-BTC). The improvement of gravimetric uptake in M-Cu-BTC (where M = Ni~(2+), Zn~(2+), and Fe~(2+)) is probably due to the increase in binding enthalpy of H_(2) with the unsaturated metal sites after the partial exchange from Cu~(2+) to other metal ions. The higher charge density of metal ions strongly polarizes hydrogen and provides the primary binding sites inside the pores of Cu-BTC and subsequently enhances the gravimetric uptake of hydrogen.