Tunable Catalytic Performance of Palladium Nanoparticles for H2O2 Direct Synthesis via Surface-Bound Ligands

There is a critical need for sustainable routes to produce hydrogen peroxide, H2O2. A promising approach involves direct synthesis from molecular hydrogen and oxygen at (sub)­ambient temperatures using unmodified supported Pd catalysts, which are limited by low selectivities. Controlling the environment of Pd active sites via surface ligands is shown to enhance selectivity. Trends among a myriad of surface ligands (i.e., phosphines, thiols, weakly bound molecules) suggest that those containing H-bonding groups lead to the highest H2O2 production, potentially by affecting reaction energetics via H-bonding with key intermediates. These insights lay the groundwork for ligand design to achieve the optimal catalyst performance for H2O2 synthesis.