Hydrogenation of Carbon Dioxide to Formate Using a Cadmium-Based Metal–Organic Framework Impregnated with Nanoparticles

Abstract

The burning of fossil fuels to meet energy demands has increased carbon dioxide (CO2) in the atmosphere, causing global warming and associated climate change. Therefore, new materials are being developed to capture CO2 effectively, limit its impact on the environment, and store and/or utilise it as an abundant C1 building block. In this study, we investigate a cadmium(II) metal–organic framework, [Cd(bdc)(DMF)]n (MOF1), synthesised by treating benzene-1,4-dicarboxylic acid with four equivalents of [Cd(NO3)2]. MOF1 was then used to support Pd, Ni, and Pt nanoparticles in forming MOF1/Pd MOF1/Ni and MOF1/Pt, respectively. These MOF-based materials were characterised using powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR), energy-dispersive X-ray spectroscopy (EDX), selected area electron diffraction (SAED), and high-resolution transmission electron microscopy (HR-TEM). MOF1/Pd MOF1/Ni and MOF1/Pt proved highly active in the catalytic hydrogenation of CO2 to formate selectively; in contrast, MOF1 did not hydrogenate CO2 to formate. The MOF1/Pd, MOF1/Ni, and MOF1/Pt catalysts produced formate selectively, with the highest TON of 1500 (TOF of 69 h−1) achieved using MOF1/Pd as the catalyst at 170 °C within 2 h. A formate yield of 98% was obtained, which demonstrates that the combination of nanoparticles and MOFs greatly enhances the catalytic activity of the active sites.

Selective Cu and Ni-MOFs as pre-catalysts for the hydrogenation of furfural to furfuryl alcohol

“…43,44 MOF 1 and MOF 2 were activated by soaking the crystals in ethanol at room temperature for 36 hours, during which ethanol was refreshed after every 6 hours followed by drying under vacuum for 24 hours at 100 °C. 45–47 Complete removal of the solvent molecules in activated MOF 1 and MOF 2 was confirmed by TGA analysis which exhibited no weight loss until decomposition (Fig. 4).…”

A novel copper-based metal-organic framework: Synthesis, characterization and evaluation for the hydrogenation of furfural to furfuryl alcohol

“…Cu-MOF was activated by soaking the framework in ethanol at room temperature for 36 hours and then dried in vacuo at 100°C for 24 hours [24,25]. TGA data that showed no weight loss until decomposition [25], proved that all of the guest molecules in activated Cu-MOF had been completely removed (Fig.…”