Ligand-Engineered CuO/Cu2O Heterointerfaces on Metal–Organic Framework-Derived Carbon-Zeolite Hybrids for Enhanced Oxygen Activation in Low-Temperature Toluene Oxidation

Developing highly efficient catalysts for the low-temperature oxidation of volatile organic compounds (VOCs) remains a significant challenge, particularly in regulating the electronic structure of transition metal sites. In this study, we demonstrate that the topological design of Cu-MOF precursors is associated with distinct interfacial electronic reconstruction of derived carbon-zeolite hybrid catalysts (Cu/C-Y). By systematically comparing four ligands-specific precursors (H3BTC, H2BDC, H2IPA, and H2DHTP), we tailored the local microenvironments and electronic configurations of the resulting Cu species. Specifically, the symmetric planar H2BDC-derived precursor system favors the formation of a representative electron-deficient CuO/Cu2O heterointerface during pyrolysis. Density functional theory (DFT) calculations reveal that this ligand-engineered architecture induces substantial interfacial charge redistribution, upshifting the Cu d-band center and reducing the oxygen vacancy formation energy from +1.88 eV to -2.11 eV. These are consistent with enhanced oxygen activation required for the possible contributions from L-H-like and MvK-like pathways. Consequently, the optimal Cubdc/C-Y catalyst exhibits superior catalytic activity for toluene oxidation (T90 = 254 °C) and an exceptionally low apparent activation energy (41.9 kJ mol-1), while maintaining good long-term stability and largely reversible water tolerance. These results provide a fundamental strategy for leveraging ligand-directed electronic programming to design advanced environmental catalysts.