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Manganese-based metal–organic frameworks (MOFs) metalated with Rh were used as pre-catalysts for CO2 hydrogenation. Activated in situ (80 % H2, 20 % CO2, 350°C), the resulting templated catalysts displayed CO2 conversion of up to 20 %, with CH4 as the main product. Used catalysts were compared with samples templated in 5 % H2/Ar at 350°C using powder X-ray diffraction, electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy. It was found that under reducing atmosphere Rh0 nanoparticles formed and organic MOF components decomposed, which allowed growth of MnO or MnCO3 and the formation of a mesh of catalytic Rh0 nanoparticles.

In Situ MOF-Templating of Rh Nanocatalysts under Reducing Conditions