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The selective oxidation of styrene with highly efficient, environmentally benign, and cost-effective catalysts are of great importance for sustainable chemical processes. Here, we develop an in situ self-assembly strategy to decorate Cu-based metal-organic framework (MOF) Cu-BDC-NH2 nanocrystals on Cu2O octahedra to construct a series of Cu2O@Cu-BDC-NH2 catalysts for selective oxidation of styrene. Using H2O2 as green oxidants, the optimized sample of Cu2O@Cu-BDC-NH2-8h could achieve 85% styrene conversion with 76% selectivity of benzaldehyde under a mild condition of 40 °C. The high performance of the as-prepared heterogeneous catalysts was attributed to the well-designed Cu+/Cu2+ interface between Cu2O and Cu-BDC-NH2 as well as the porous MOF shells composed of the uniformly dispersed Cu-BDC-NH2 nanocrystals. The alkaline properties of Cu2O and the –NH2 modification of MOFs enable the reaction to be carried out in a base-free condition, which simplifies the separation process and makes the catalytic system more environmentally friendly. Besides the Cu2O octahedra (od-Cu2O), the Cu2O cuboctahedrons (cod-Cu2O) were synthesized by adjusting the added polyvinyl pyrrolidone, and the obtained cod-Cu2O@Cu-BDC-NH2 composite also showed good catalytic performance. This work provides a useful strategy for developing highly efficient and environmentally benign heterogeneous catalysts for the selective oxidation of styrene.

Metal-Organic Frameworks Decorated Cu2O Heterogeneous Catalysts for Selective Oxidation of Styrene