Review on supported metal catalysts with partial/porous overlayers for stabilization

Heterogeneous catalysts of supported metals are important for both liquid-phase and gas-phase chemical transformations which underpin the petrochemical sector and manufacture of bulk or fine chemicals and pharmaceuticals. Conventional supported metal catalysts (SMC) suffer from deactivation resulting from sintering, leaching, coking and so on. Besides the choice of active species (e.g. atoms, clusters, nanoparticles) to maximize catalytic performances, strategies to stabilize active species are imperative for rational design of catalysts, particularly for those catalysts that work under heated and corrosive reaction conditions. The complete encapsulation of metal active species within a matrix (e.g. zeolites, MOFs, carbon, etc.) or core-shell arrangements is popular. However, the use of partial/porous overlayers (PO) to preserve metals, which simultaneously ensures the accessibility of active sites through controlling the size/shape of diffusing reactants and products, has not been systematically reviewed. The present review identifies the key design principles for fabricating supported metal catalysts with partial/porous overlayers (SMCPO) and demonstrates their advantages versus conventional supported metals in catalytic reactions.