Synthesis and application of a MOF-derived Ni@C catalyst by the guidance from an in situ hot stage in TEM

Abstract

Metal–organic frameworks (MOFs) as a class of crystalline porous solids have attracted considerable attention due to their promising potential performance. MOFs have been recently proved to be ideal sacrificial templates for fabricating their respective derivatives by changing the thermal conditions. However, uncertainties still remain, and the direct observation of transition from MOF to metal nanoparticles (NPs) dispersed in carbon matrix is an important and crucial task for the development of MOF-derived materials. Here, transmission electron microscopy (TEM) combined with in situ hot stage technique was applied to directly observe the transition from MOF to metal NPs. Through in situ TEM experiment, the nanocrystals of Ni–ntca precursor (ntca = 1,4,5,8-naphthalenetetra carboxylic acid) are pyrolyzed under the temperature of 400, 500, or 600 °C to synthesize abundant Ni-NPs embedded in hierarchically porous carbon composites. Furthermore, the as-prepared samples show high catalytic activity and stability for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with NaBH₄ in aqueous conditions. More importantly, Ni@C-600, which has nickel contents of 72.8%, shorten the reduction time to 3.5 min with high conversion of nearly 100%. When the catalyst is applied to recycle after being separated from the reaction by an extern magnet, it still keeps high conversion of 92% after 8 cycles, addressing the high stability of the composites. It is believed that these results will further facilitate the exploration of the technique of the TEM combined with in situ hot stage as a powerful tool in the carbonization of MOFs to obtain MOF-derived materials with different applications.