Semi-solid and solid frustrated Lewis pair catalysts

Abstract

Recently discovered homogeneous frustrated Lewis pairs (FLPs) have attracted much attention for metal-free catalysis due to their promising potential for the activation of small molecules (e.g., H2, CO, CO2, NOx and many others). Hence, a wide range of these homogeneous FLPs have been extensively explored for many advanced organic syntheses, radical chemistry and polymerizations. In particular, these FLPs are efficiently utilized for the hydrogenation of various unsaturated substrates (e.g., olefins, alkynes, esters and ketones). Inspired by the substantial progress in these homogeneous catalytic systems, heterogeneous FLP catalysts, including semi-solid and all-solid catalysts, have also emerged as an exciting and evolving field. In this review, we highlight the recent advances made in heterogeneous FLP-like catalysts and the strategies to construct tailorable interfacial FLP-like active sites on semi-solid and all-solid FLP catalysts. Challenges and outlook for the further development of these catalysts in synthetic chemistry will be discussed.

Bismuth atom tailoring of indium oxide surface frustrated Lewis pairs boosts heterogeneous CO2 photocatalytic hydrogenation

“…Besides catalyst modifications designed to broaden spectral response and improve charge transfer efficiency, it is also important to accelerate conversion rates of H 2 or CO 2 on specially designed surface sites to boost photon and energy efficiency. Recently, surface frustrated Lewis pairs (SFLPs) have shown a propensity towards H 2 dissociation and CO 2 activation, a key enabler for many catalytic reactions, including hydrogenation, hydroamination and CO 2 reduction [8][9][10] . Generally speaking, SFLPs comprise proximal Lewis acidic and Lewis basic sites providing synergetic activation of reactant molecules.…”

Holey Lamellar High‐Entropy Oxide as an Ultra‐High‐Activity Heterogeneous Catalyst for Solvent‐free Aerobic Oxidation of Benzyl Alcohol

“…Fort he vacancy-abundant holey lamellar HEO,m any metal ions are exposed on the surface of the material, and the electrostatic potential near these metal ions is positive.W hent he À OH group of benzyl alcohol approaches,t he Hc ombines with the surface oxygen by hydrogen bond, and the Oc ombines with the positively charged metals through metal-oxygen bond, greatly increasing the adsorption energy. [41,42] However,f or bulk HEO,t he O À H•••O angle is too small to form hydrogen bond (Supporting Information, Figure S12). Thus,Hin benzyl alcohol molecule cannot form hydrogen bond with surface oxygen on bulk HEO as the case in holey HEO.…”

Reaction mechanisms at the homogeneous–heterogeneous frontier: insights from first-principles studies on ligand-decorated metal nanoparticles

“…67 N-containing compounds can also play an important role in hydrogenation reactions via the so-called frustrated Lewis pair (FLP) activity. 68 FLP-type mechanisms in heterogeneous catalysis 69 typically involve the organic ligand as a Lewis base and the metal surface as a Lewis acid. Such approach is commonly employed in Au-based catalysts 70 to overcome their inertness towards H 2 activation.…”