Modification of boron nitride nanocages by titanium doping results unexpectedly in exohedral complexes

Ruyi Li,Yang Wang

doi:10.1038/s41467-019-12877-0

Abstract

Despite their early experimental production and observation, the unambiguous molecular structures of metal-containing boron nitride (BN) nanocages still remain mysterious. It has been commonly assumed that this family of compounds has the metal atom confined inside the cage, just like their isoelectronic cousins, carbon metallofullerenes do. Here, we demonstrate that Ti(BN)n (n = 12–24) complexes have, unexpectedly, an exohedral structure instead of an endohedral one, which could be verified by collision-induced dissociation experiments. The predicted global minimum structures exhibit some common bonding features accounting for their high stability, and could be readily synthesized under typical conditions for generating BN nanoclusters. The Ti doping dramatically changes not only the cage topology, but the arrangement of B and N atoms, endowing the resultant compounds with potential for {mathrm{CO}}_{2} capture and nitrogen fixation. These findings may expand or alter the understanding of BN nanostructures functionalized with other transition metals.

Highlights

Despite their early experimental production and observation, the unambiguous molecular structures of metal-containing boron nitride (BN) nanocages still remain mysterious
BN fullerenes, in particular, have been synthesized by electron irradiation[8,9] or arc-melting[10,11] methods, with their chemical compositions and cage-like structures identified by time-of-flight mass spectrometry and transmission electron microscopy
Unlike carbon fullerenes whose cage framework is usually built of pentagons and hexagons, a BN fullerene consists of squares, hexagons[18], and sometimes octagons for larger cages[19]

Summary

Introduction

Despite their early experimental production and observation, the unambiguous molecular structures of metal-containing boron nitride (BN) nanocages still remain mysterious. We show that BN fullerenes doped with a single Ti atom in general have an exohedral structure, at least for cage sizes comparable to their experimentally observed carbon counterparts, Ti@C2n26.

Results

Conclusion