Organoboron‐Functionalized Metal‐organic Nanosheets for Highly Efficient CO2 Fixation Mediated by Frustrated Lewis Pairs

Converting CO2 to high‐value fine chemicals represents one of the most promising approaches to combat global warming and subsequently achieve a sustainable carbon cycle. Herein, we contribute an organoboron functionalized ultra‐thin metal‐organic nanosheet (MON), termed TCPB‐Zr‐NS, featuring an abundance of exposed Lewis acidic B and formate sites, which can effectively promote CO2 conversion upon the addition of Lewis basic o‐phenylenediamines. Compared with the prototypical 3D analogue TCPB‐Zr‐3D, the resultant TCPB‐Zr‐NS showcases dramatically improved catalytic activity for the cyclization of o‐phenylenediamine as a result of the highly exposed active sites and efficient substrates/products diffusion. Strikingly, the incorporation of Lewis acidic B sites into ultra‐thin Zr‐based MON (Zr‐MON) not only promotes the highly efficient CO2 conversion, but also enhances the recyclability/durability of catalysts. Additionally, the underlying catalytic mechanism has been well established by the comprehensive experiments and theoretical calculations, unveiling a formate‐assisted frustrated Lewis pairs (FLP) mediated catalytic pathway. This work opens up a new avenue to heterogeneous FLP‐based catalysts for small molecule activation and beyond.