A Mo-based MOF is an efficient electrocatalyst for the N2 reduction reaction with a low overpotential of 0.18 V.

Xiao and colleagues successfully designed a powerful siliceous zeolite support and a core-shell structure, which is achieved by fixing RhMn nanoparticles within Silicate-1 zeolite crystals (RhMn@S-1), could remarkably boost the ethanol production from direct syngas conversion. C 2 -oxygenate selectivity of 88.3% in the total oxygenates was obtained at 42.4% CO conversion, decidedly outperforming the previous Rh-based catalysts. This work provides a new route for design and preparation of highly efficient catalyst for ethanol production from syngas.

Embedding metal species into zeolite frameworks can create framework-bond metal sites in a confined microenvironment. The metals sitting in the specific T sites of zeolites and their crystalline surroundings are both committed to the interaction with the reactant, participation in the activation, and transient state achievement during the whole catalytic process. Herein, we construct isolated Co-motifs into purely siliceous MFI zeolite frameworks (Co-MFI) and reveal the location and microenvironment of the isolated Co active center in the MFI zeolite framework particularly beneficial for propane dehydrogenation (PDH). The isolated Co-motif with the distorted tetrahedral structure ({(SiO)2Co­(HO–Si)2}, two Co–O–Si bonds, and two pseudobridging hydroxyls (Co···OH–Si) is located at T1(7) and T3(9) sites of the MFI zeolite. DFT calculations and deuterium-labeling reactions verify that the isolated Co-motif together with the MFI microenvironment collectively promotes the PDH reaction by providing an exclusive microenvironment to preactivate C3H8, polarizing the oxygen in Co–O–Si bonds to accept H* ({(SiO)­CoHδ− (Hδ+O–Si)3}), and a scaffold structure to stabilize the C3H7* intermediate. The Co-motif active center in Co-MFI goes through the dynamic evolutions and restoration in electronic states and coordination states in a continuous and repetitive way, which meets the requirements from the series of elementary steps in the PDH catalytic cycle and fulfills the successful catalysis like enzyme catalysis.