Finding Natural, Dense, and Stable Frustrated Lewis Pairs on Wurtzite Crystal Surfaces

TL;DR

This study identifies naturally occurring, dense, and stable frustrated Lewis pairs on wurtzite crystal surfaces, enabling efficient activation of small molecules without complex construction processes.

Contribution

It reveals that wurtzite-structured crystals naturally host dense and stable SFLPs on specific surfaces, simplifying their development for catalytic applications.

Findings

SFLPs naturally exist on (100) and (110) surfaces of wurtzite crystals.

Surface density of SFLPs reaches 7.26 x 10^14 cm^-2.

SFLPs remain stable under high temperatures and reactive atmospheres.

Abstract

The surface frustrated Lewis pairs (SFLPs) open up new opportunities for substituting noble metals in the activation and conversion of stable molecules. However, the applications of SFLPs on a larger scale are impeded by the complex construction process, low surface density, and sensitivity to the reaction environment. Herein, wurtzite-structured crystals such as GaN, ZnO, and AlP are found for developing natural, dense, and stable SFLPs. It is revealed that the SFLPs can naturally exist on the (100) and (110) surfaces of wurtzite-structured crystals. All the surface cations and anions serve as the Lewis acid and Lewis base in SFLPs, respectively, contributing to the surface density of SFLPs as high as 7.26 x 1014 cm-2. Ab initio molecular dynamics simulations indicate that the SFLPs can keep stable under high temperatures and the reaction atmospheres of CO and H2O. Moreover, outstanding performance for activating the given small molecules is achieved on these natural SFLPs, which originates from the optimal orbital overlap between SFLPs and small molecules. Overall, these findings not only provide a simple method to obtain dense and stable SFLPs but also unfold the nature of SFLPs toward the facile activation of small molecules.