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Updated: Jul 11, 2025

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Low-temperature hydroformylation of ethylene by phosphorous stabilized Rh sites in a one-pot synthesized Rh-(O)-P-MFI
Minjie Zhao1, Chengeng Li1,2, Daviel Gómez1
1Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas (UPV-CSIC), Avenida de los Naranjos s/n, 46022, Valencia, Spain.
Abstract:
Zeolites containing Rh single sites stabilized by phosphorous were prepared through a one-pot synthesis method and are shown to have superior activity and selectivity for ethylene hydroformylation at low temperature (50 °C). Catalytic activity is ascribed to confined Rh2O3 clusters in the zeolite which evolve under reaction conditions into single Rh3+ sites. These Rh3+ sites are effectively stabilized in a Rh-(O)-P structure by using tetraethylphosphonium hydroxide as a template, which generates in situ phosphate species after H2 activation. In contrast to Rh2O3, confined Rh0 clusters appear less active in propanal production and ultimately transform into Rh(I)(CO)2 under similar reaction conditions. As a result, we show that it is possible to reduce the temperature of ethylene hydroformylation with a solid catalyst down to 50 °C, with good activity and high selectivity, by controlling the electronic and morphological properties of Rh species and the reaction conditions.
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