Electronic Modulation and Active Site Exposure Using C60 Fullerenolamine Enable High-Performance Alcohol Oxidation on Pd Metallene Catalysts.

The availability of active sites and the electronic structure of metal heterogeneous catalysts are crucial to maximize their catalytic performance. In this study, we describe a new and efficient catalyst system, C60 fullerenolamine (FA)-modified Pd metallene (Pdene), and demonstrate that the FA molecules not only increase the active sites availability but also exert an electronic effect that enhances the catalytic performance of Pdene in alcohol oxidation reactions. Specifically, FA increases the electrochemical active surface area through dispersion, while its electron-withdrawing characteristics induce an electron-deficient surface on Pdene, which facilitates the adsorption of electron-rich intermediates (OH*) and the desorption of electron-deficient poisonous intermediates (CO*). The practical significance of this modification is demonstrated by achieving a 54.5% increase in mass activity and 46.3% enhancement in specific activity for ethanol oxidation relative to Pdene. Beyond these improvements, the FA-Pdene catalyst demonstrates exceptional operational stability, superior CO poisoning resistance, and enhanced C1 pathway selectivity. An in-depth analysis utilizing in-situ Fourier transform infrared spectroscopy, coupled with density functional theory calculations, offers valuable insights into how the FA ligand modulates the mechanistic pathways involved in ethanol oxidation processes. This fullerene-mediated catalytic effect could hold the key to unlocking the potential of the metal-based system.