C₁ Chemistry on Metal Carbide Nanoparticles: Boosting the Conversion of CO₂ and CH₄

The studies described in this Perspective show that transition metal carbide (TMC) nanoparticles can be very useful for the activation of three molecules located at the heart of C₁ chemistry: H₂, CH₄, and CO₂. They also can play a major role in the trapping and conversion of two major greenhouse gases. A combination of experiment and theory has shed light on the physical and chemical properties of these systems, which can be very different from those of bulk carbides. Molecular clusters of these compounds, which can be inserted inside the cages of zeolites or carbon nanotubes, have unsaturated metal and carbon atoms that frequently work in a cooperative way when dealing with hard-to-activate molecules, such as CH₄ and CO₂. These molecular clusters can evolve into nanoparticles of small to medium size (<15 nm) that have unique carbon/metal ratios and structures not seen in the bulk metal carbides. Even when their structures are cuts from bulk lattices, the TMC nanoparticles have corner or edge atoms that are active for the cleavage and conversion of C-H and C-O bonds. Here, we cover experimental and theoretical studies with well-defined metal carbide nanoparticles prepared by different methods, free and supported on diverse substrates. The Perspective ends with a discussion of current challenges and potential applications.