Effective activation of CO2 is a prerequisite for efficient utilization of CO2 in organic synthesis. Precisely controlling the interfacial events of solids shows potential for activation. Herein, defect-enriched CeO2 with constructed interfacial frustrated Lewis pairs (FLPs, two adjacent Ce3+···O2–) effectively activates CO2 via the interactions between C/Lewis basic lattice O2– and the two O atoms in CO2/two adjacent Lewis acidic Ce3+ ions. Selective cyclic carbonate production from a catalytically tandem protocol of olefins and CO2 is used to demonstrate FLP-inspired CO2 activation.

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.

Pristine Ru generally shows unsatisfying activity for the electrocatalytic hydrogen evolution reaction (HER). How to activate its HER activity through facile methodologies is very challenging. Recently, metal-supported electrocatalysts integrating metals with efficient hydrogen adsorption and supports with facile hydrogen desorption delivered a high HER performance through a metal-to-support hydrogen spillover process, where the small metal–support work function difference (ΔΦ) was identified as the criterion for the successful interfacial hydrogen spillover. Herein, we demonstrate that a hydrogen spillover strategy significantly boosts the HER activity of Ru by depositing a Ru1Fe1 alloy on CoP (Ru1Fe1/CoP) with a small ΔΦ of 0.05 eV. Experimentally, Ru1Fe1/CoP (0.7 wt % Ru loading) delivered a high Ru utilization activity of 139.8 A/mgRu and a long-term durability in acid. Mechanism investigations authenticated that the small ΔΦ guaranteed the interfacial hydrogen spillover from Ru1Fe1 with efficient hydrogen adsorption to CoP with facile hydrogen desorption and thereafter boosted the HER activity of Ru.

Carbon neutrality initiative has stimulated the development of the sustainable methodologies for hydrogen generation and safe storage. Aqueous-phase reforming methanol and H2O (APRM) has attracted the particular interests for their high gravimetric density and easy availability. Thus, to efficiently release hydrogen and significantly suppress CO generation at low temperatures without any additives is the sustainable pursuit of APRM. Herein, we demonstrate that the dual-active sites of Pt single-atoms and frustrated Lewis pairs (FLPs) on porous nanorods of CeO2 enable the efficient additive-free H2 generation with a low CO (0.027%) through APRM at 120 °C. Mechanism investigations illustrate that the Pt single-atoms and Lewis acidic sites cooperatively promote the activation of methanol. With the help of a spontaneous water dissociation on FLPs, Pt single-atoms exhibit a significantly improved reforming of *CO to promote H2 production and suppress CO generation. This finding provides a promising path towards the flexible hydrogen utilizations.

The highest catalytic performance of Ni0.5Co0.5@NC catalysts can be attributed to their optimized electronic structure to facilitate the hydrogen activation.

A highly-dispersed Pt/CeO2 catalyst synthesized through a spontaneous surface redox reaction between metal ions and Ce(OH)3/CeO2 nanorods delivers high CO oxidation activity.

Adsorption of molecules on active sites of heterogeneous catalysts significantly affects their catalytic performance, which provides a perspective to understand the catalytic process/mechanism at the atomic level and to establish structure–function relationships. This Perspective illustrates a strong correlation between the adsorption of reactants on CeO2-based catalysts and their improved catalytic activity and/or selectivity for various transformations. Regulating the oxygen defect of CeO2 provides an effective approach to construct two typical active sites of a frustrated Lewis pair (FLP) and dual-active site. Benefiting from the unique spatial and electronic structures, the FLP sites exhibit an “embedded” adsorption configuration of small molecules, promoting their effective activation and transformation. The dual-active sites constructed by metal clusters and oxygen vacancy of CeO2 could break the competitive adsorption of various molecules and thereafter enable highly active and selective hydrogenations. Finally, the possibilities and challenges in the adsorption behaviors of various molecules on CeO2-based catalysts are outlined. The tailorability of adsorption strength and selective configuration of molecules on active sites are anticipated to stimulate and guide the design of high-performing catalysts.

Hydrogen spillover on heterogeneous catalysts offers a new opportunity to improve catalytic hydrogenation. Due to the slow migration of hydrogen under mild conditions, hydrogen spillover-improved hydrogenation is still unsatisfactory on carbon material-supported metal nanoparticles. Herein, the modifying interface of carbon support-stimulated hydrogen spillover for hydrogenation has been successfully identified on the dual-active sites of Pt nanoparticles and modified carbon black (Pt/C–H2O2). The oxygen-containing-group-modified carbon black, which was achieved by a commonly used H2O2 treatment, not only triggered the efficient hydrogen migration along the carbon supports but also enhanced the adsorption of polar substrates, thus affording simultaneously enhanced catalytic activity and selectivity as well as stability. For probe reaction of 6-chloroquinoline hydrogenation to 6-chloro-1,2,3,4-tetrahydroquinoline, Pt/C–H2O2 catalysts yielded a 6.1 times higher catalytic activity with a high selectivity >99.5% than that on Pt/C with selectivity <96.0%. This work is anticipated to provide a facile and effective methodology for fabricating highly performed hydrogenation heterogeneous catalysts.