A General Strategy for Constructing Two-Dimensional MOFs in Ethylene Glycol: Application in Tandem Conversion of Styrene and CO ₂

Two-dimensional (2D) metal organic frameworks (MOFs) combine tunable metal nodes and organic linkers with the topological advantages of 2D, offering high surface area and accessible active sites for catalysis. However, developing a general and controllable synthetic strategy for these materials remains challenging. Here, ethylene glycol is employed as a soft template to generate an extensive library of 2D MOFs, including Ni-based (NiBDC, NiABDC, NiDOBDC, NiBPDC), M-BDC (MnBDC, CoBDC, ZrBDC, ZnBDC), and bimetallic systems (NiMnBDC, NiCoBDC, NiMnBPDC). These materials were further evaluated for the atom-economic tandem conversion of styrene and CO 2 into cyclic carbonates under mild conditions─an important route for CO 2 utilization in which efficient catalysts remain scarce and mechanistic understanding remains limited. The experimental results show that all Ni-based MOFs exhibit high catalytic performance, affording carbonate yields of 85.4–94.5% in the presence of TBAB. Guided by combined DFT calculations and the above experimental data, a bimetallic NiMnBDC catalyst was rationally designed to integrate the high surface area and structural stability of NiBDC with the redox flexibility of Mn. This catalyst achieves 92.1% conversion of styrene within only 4 h under solvent-free and cocatalyst-free mild conditions, demonstrating outstanding activity. Overall, this work not only establishes a general approach to 2D MOF synthesis but also delivers a detailed mechanistic insight into the catalytic pathway, enabling rational optimization of catalysts for tandem styrene-CO 2 transformation.