Disclosing the Role of Gold on Palladium – Gold Alloyed Supported Catalysts in Formic Acid Decomposition

Herein, we report the synthesis of preformed bimetallic Pd‐Au nanoparticles supported on carbon nanofibers with different Pd : Au atomic ratio (nominal molar ratio: 8–2, 6–4, 4–6, 2–8) and the corresponding Pd and Au monometallic catalysts by sol immobilization method. The obtained materials were characterized thoroughly by Transmission Electron Microscopy (TEM), X‐ray photoelectron spectroscopy (XPS) and inductively coupled plasma optical emission spectroscopy (ICP‐OES). The catalytic performances of the Pd‐Au catalysts were evaluated in the aqueous phase dehydrogenation of formic acid (FA) at room temperature obtaining enhanced activity, stability and selectivity compared to the monometallic systems. In particular, Pd6Au4 and Pd8Au2 showed the best combination of catalytic properties, i. e., high selectivity to H2 and improved catalytic stability. Density functional theory (DFT) calculations on Pd15, Au15 and Pd9Au6 clusters supported on a carbon sheet were then simulated to provide atomic level understanding to the beneficial effect of gold observed in the experimental results. Au15 barely adsorb FA, while Pd15 possesses an adsorption energy higher than Pd9Au6. Dehydrogenation and dehydration pathways were followed on all these models. For Pd9Au6, the most favourable route was the formation of carbon dioxide and hydrogen. Analysis of the electronic structures was also performed on the different models showing a stronger interaction between the bimetallic system and the support proving the alloy superior stability. Dynamic duo: DFT and experimental data were employed to disclose the role of gold in palladium‐based catalyst during the aqueous‐phase formic acid decomposition. Pd6Au4 and Pd8Au2 showed the best catalytic properties: high H2 selectivity and increased stability. DFT calculations on Pd15, Au15 and Pd9Au6 clusters supported on a graphitized carbon were simulated. Dehydrogenation and dehydration pathways were studied and, for Pd9Au6 the most exothermic route was the dehydrogenation. Moreover, Pd9Au6 exhibited a stronger interaction with the carbon proving its superior stability.