Conductive catalysis by subsurface transition metals

Abstract

The nature of catalysis is being hotly pursued for over a century, and current research is focused on understanding active centers and their electronic structures. Herein, the concept of conductive catalysis is proposed and verified by theoretical simulations and experimental observations. Metallic systems containing buried catalytically active transitional metals and exposed catalytically inert main group metals are constructed, and the electronic interaction between them via metallic bonding is disclosed. Through the electronic interaction, the catalytic properties of subsurface transitional metals (Pd or Rh) can be transferred to outermost main group metals (Al or Mg) for several important transformations like semi-hydrogenation, Suzuki-coupling and hydroformylation. The catalytic force is conductive, in analogy with the magnetic force and electrostatic force. The traditional definition of active centers is challenged by the concept of conductive catalysis and the electronic nature of catalysis is more easily understood. It might provide new opportunities for shielding traditional active centers against poisoning or leaching and allow for precise regulation of their catalytic properties by the conductive layer.

Catalysis by subsurface metal atoms in Al(001) through electron transfer

“…Recently, Professor Landong Li from Nankai University and colleagues reported unique metallic systems containing buried catalytically active transitional metals and exposed catalytically inert main group metals [ 3 ], which exhibited remarkable performance in a variety of reactions such as alkyne semi-hydrogenation, olefin hydroformylation and Suzuki-coupling reactions, revealing the effective conduction of catalytic properties through metallic bonding. Inspired by the disappearance of surface transitional metal species on aluminum substrate upon annealing, density functional theory (DFT) calculations were conducted by the team.…”

“… The semi-hydrogenation of acetylene and propylene hydroformylation over Pd/Al and Rh/Al in the conductive catalytic system, respectively, with Pd or Rh atoms completely buried in the subsurface of Al substrate [ 3 ]. …”