Hydrogenation of Carbon Dioxide to Formate by Noble Metal Catalysts Supported on a Chemically Stable Lanthanum Rod-Metal-Organic Framework
Artikel i vetenskaplig tidskrift, 2023

Cyclometalated with platinum-groupmetals, the La-MOF JMS-5with a bipyridyl dicarboxylate linker gave a TON of over 5000 forIr-(III) and over 4000 for Rh-(III) in the catalytic hydrogenation ofcarbon dioxide to formate without any signs of nanoparticles. Fullcharacterization was performed including XPS, TEM, PXRD, and gas sorption.Single crystal diffraction revealed an unusual rod-MOF topology. The conversion of carbon dioxide to formate is of greatimportancefor hydrogen storage as well as being a step to access an array ofolefins. Herein, we have prepared a JMS-5 metal-organic framework(MOF) using a bipyridyl dicarboxylate linker, with the molecular formula[La-2(bpdc)(3/2)(dmf)(2)(OAc)(3)]center dot dmf. The MOF was functionalized by cyclometalation using Pd-(II),Pt-(II), Ru-(II), Rh-(III), and Ir-(III) complexes. All metal catalystssupported on JMS-5 showed activity for CO2 hydrogenationto formate, with Rh-(III)@JMS-5a and Ir-(III)@JMS-5a yielding 4319 and5473 TON, respectively. X-ray photoelectron spectroscopy of the mostactive catalyst Ir-(III)@JMS-5a revealed that the iridium binding energiesshifted to lower values, consistent with formation of Ir-Hactive species during catalysis. The transmission electron microscopyimages of the recovered catalysts of Ir-(III)@JMS-5a and Rh-(III)@JMS-5adid not show any nanoparticles. This suggests that the catalytic activityobserved was due to Ir-(III) and Rh-(III). The high activity displayedby Ir-(III)@JMS-5a and Rh-(III)@JMS-5a compared to using the Ir-(III)and Rh-(III) complexes on their own is attributed to the stabilizationof the Ir-(III) and Rh-(III) on the nitrogen and carbon atom of theMOF backbone.


Maureen Gumbo

University of Johannesburg

Midlands State University

Banothile C. E. Makhubela

University of Johannesburg

Francoise Mystere Amombo Noa

Chalmers, Kemi och kemiteknik, Kemi och biokemi

Lars Öhrström

Chalmers, Kemi och kemiteknik, Kemi och biokemi

Bassem Al-Maythalony

Royal Sci Soc

G. Mehlana

Midlands State University

Inorganic Chemistry

0020-1669 (ISSN) 1520-510X (eISSN)

Vol. 62 23 9077-9088


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