Zr-Based MOF-545 Metal-Organic Framework Loaded with Highly Dispersed Small Size Ni Nanoparticles for CO₂ Methanation

We report the use of Zr-based metal-organic frameworks (MOFs) MOF-545 and MOF-545(Cu) as supports to prepare catalysts with uniformly and highly dispersed Ni nanoparticles (NPs) for CO₂ hydrogenation into CH₄. In the first step, we studied the MOF support under catalytic conditions using operando diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, ex situ characterizations (PXRD, XPS, TEM, and EDX-element mapping), and DFT calculations. We showed that the high-temperature conditions undoubtedly confer a potential for catalytic functionality to the solids toward CH₄ production, while no role of the Cu could be evidenced. The MOF was shown to be transformed into a catalytically active material, amorphized but still structured with dehydroxylated Zr-oxoclusters, in line with DFT calculations. In the second step, Ni@MOF-545 catalysts were prepared using either impregnation (IM) or double solvent (DS) methods, followed by a dry reduction (R) route under H₂ to immobilize Ni NPs. The highest catalytic activity was obtained with the Ni@MOF-545 DS R catalyst (595 mmol_CH4 g_Ni^-1 h^-1) with 100% CH₄ selectivity and 60% CO₂ conversion after ∼3 h. The higher catalytic activity of Ni@MOF-545 DS R is a result of much smaller (∼5 nm) and better dispersed Ni NPs than in the IM sample (20-40 nm), the latter exhibiting sintering. The advantages of the encapsulation of Ni NPs by the DS method and of the use of a MOF-545-based support are discussed, highlighting the interest of designing yet-unexplored Zr-based MOFs loaded with Ni NPs for CO₂ hydrogenation.