Fabrication of a High-Quality, Porous, Surface-Confined Covalent Organic Framework on a Reactive Metal Surface.

A major goal of heterogeneous catalysis is to optimize catalytic selectivity. Selectivity is often limited by the fact that most heterogeneous catalysts possess sites with a range of reactivities, resulting in the formation of unwanted by-products. The construction of surface-confined covalent organic frameworks (sCOFs) on catalytically active surfaces is a desirable strategy, as pores can be tailored to operate as catalytic nanoreactors. Direct modification of reactive surfaces is impractical, because the strong molecule-surface interaction precludes monomer diffusion and formation of extended architectures. Herein, we describe a protocol for the formation of a high-quality sCOF on a Pd-rich surface by first fabricating a porous sCOF through Ullmann coupling on a Au-rich bimetallic surface on Pd(111). Once the sCOF has formed, thermal processing induces a Pd-rich surface while preserving the integrity of the sCOF architecture, as evidenced by scanning tunneling microscopy and titration of Pd sites through CO adsorption.