(544hm) Catalytic Hydrogenation of Carbon Monoxide to Formaldehyde in Functionalized Metal Organic Frameworks: An Investigation of Pathway

Zhang, S., University of Pittsburgh
Li, L., University of Pittsburgh
Ruffley, J., University of Pittsburgh
Johnson, J. K., University of Pittsburgh
The production of formaldehyde is of great importance because of its role as platform reagent and wide application in industry. The current industrial method is a three-step process, which is energy extensive and has separation problem. However, the direct hydrogenation of CO to formaldehyde is challenging because it’s thermodynamically unfavorable1. Our previous work has shown that MOFs functionalized with Lewis pairs (LPs) have the potential to be effective catalysts for the conversion of CO2 to formic acid through direct hydrogenation2-4. Herein, we proposed a new approach to directly synthesize formaldehyde from CO and H2, by using Lewis pairs functionalized MOFs as the heterogeneous catalyst, to address the sluggish reaction kinetic and the thermodynamic limitations.

We have computed the overall reaction pathways in gas phase, inside the functionalized UiO-67, and on the LP cluster analog using the density functional theory (DFT), in addition to more advanced methods. The activation barrier of the rate-limiting step for CO hydrogenation is reduced to 1.67 eV from 3.54 eV for uncatalyzed gaseous reaction. We also did GCMC simulations to calculate adsorption isotherms for CO and H2, which show enhanced pressures for CO and H2 inside the MOF pores. Our results indicate that LPs functionalized MOF, UiO-67-NBF2, is a promising catalyst for gas-phase synthesis of formaldehyde from CO and H2, with enhanced rate and conversion, and the ease of product separation.


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