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A composite cluster with core–shell structure composed of polyoxometalates (POMs) and graphdiyne (GDY) was synthesized and applied for the electrochemical oxygen evolution reaction (OER). Compared with the original POMs and GDY, the composite cluster Co4(PW9)2@GDY demonstrates superior performance and stable electrochemical OER. The core–shell composite cluster exhibited high performance for OER with low potentials and a small Tafel slope. Moreover, high catalytic activity of the cluster was achieved at a high current density. Co4(PW9)2@GDY has excellent catalytic performance and long stability due to its strong electron-transfer ability in the system, higher conductivity, and the structural advantage of pores in GDY. We also tested the OER synergism mechanism between POM and GDY. This would open access and guide us to synthesize novel clusters based on polyoxometalates and graphdiyne. [ABSTRACT FROM AUTHOR]

In this work, the Keggin-type phosphomolybdic acid (PMo 12) is immobilized in the cavities of Zirconium metal–organic framework (UiO-67) with suitable cage size and limited windows. The PMo 12 @UiO-67 nanocomposite is used as a heterogeneous catalyst for the epoxidation of olefin with excellent retrievability. [Display omitted] • The PMo 12 @UiO-67 nanocomposite is synthesized by the phosphomolybdic acid (PMo 12) as the guest and size-mathched UiO-67 as the host through one-step hydrothermal method. • The PMo 12 @UiO-67 nanocomposite exhibits excellent catalytic activity for the epoxidation of olefin, which could be easily regenerated and recycled for five times without significant loss of catalytic activity. Polyoxometalates (POMs) as the nanocomposites have been applied as the homogeneous catalyst for some organic reactions. Choosing an appropriate support for POMs is an effective approach to solve their low-stability. In this work, the Keggin-type phosphomolybdic acid (PMo 12) is immobilized in the cavities of Zirconium metal–organic framework (UiO-67) with suitable cage size and limited windows. The nanocomposite (PMo 12 @UiO-67) is used as a heterogeneous catalyst for the epoxidation of olefin with excellent retrievability. The above result would help us to develop more polyoxometalate-base heterogeneous catalyst for the epoxidation of olefin. [ABSTRACT FROM AUTHOR]