No abstract

Small ZnO nanoclusters supported on dealuminated β zeolite were prepared and evaluated for catalyzing direct dehydrogenation of propane to propylene (PDH), exhibiting high catalytic performance. N2 sorption, XRD, TEM, 27Al and 28Si MAS NMR, IR, XRF, DR UV‐vis, XPS, and NH3‐TPD techniques were employed to characterize the physicochemical properties of this novel catalyst system. It is found that the Zn species can be accommodated in the vacant T‐atom sites of dealuminated β zeolite due to the reaction of aqueous zinc acetate solution with silanol groups, and thus, producing massive small ZnO nanoclusters as active phases in PDH. Additionally, dealuminated β zeolite can greatly depress side reactions attributable to the absence of strong acid sites, thereby guaranteeing high catalytic activity, propylene selectivity and stability. As a result, the optimal catalyst of 10 wt% Zn loaded on dealuminated β zeolite exhibits a high initial propane conversion of around 53 % and a superior propylene selectivity of about 93 % at a space velocity of 4000 cm3 gcat−1 h−1, together with the high stability and satisfactory reusability. This study may open a new way to design and synthesize highly active PDH catalysts with high selectivity and stability.

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.