Freezing Non-Equilibrium Structural Defects in Integrated Cu4MgO5/ZnO Nanocomposites for Extended Visible-Light-Driven Solar Fuel Production

The rational configuration of electronic band structures through deep-seated structural disorder remains a formidable challenge in sustainable solar-to-fuel conversion. Herein, we report a transformative kinetic strategy to “freeze” an extraordinary density of non-equilibrium structural defects within an integrated Cu4MgO5/ZnO nanocomposite. Synthesized via a chitosan-assisted coordination-combustion route followed by rapid thermal quenching, the material preserves a record crystallographic dislocation density of 1.09 × 1015 m−2 and significant lattice microstrain (1.04 × 10−3). This engineered structural disorder induces a profound reconfiguration of the electronic landscape, generating a continuous manifold of sub-bandgap “tail states” that narrow the optical bandgap to a remarkable 1.34 eV. Consequently, the defect-rich architecture facilitates unprecedented dual-channel photocatalytic performance under simulated solar irradiation in an aqueous solution containing 5 vol% triethanolamine (TEOA) as a sacrificial electron donor; the catalyst achieved a hydrogen evolution rate of 17,700.0 µmol g−1 h−1 and a methane production rate of 172.50 µmol g−1 h−1—representing a 36.3-fold and 43.1-fold enhancement over commercial ZnO, respectively. With an apparent quantum yield of 8.42% at 420 nm and robust photostability—maintaining 95.3% of its activity over five consecutive cycles (25 h total)—this noble-metal-free ternary system bypasses the limitations of traditional heterojunctions. Our findings establish a new benchmark for defect-engineered catalysts, providing a scalable blueprint for high-efficiency carbon neutrality and solar fuel production.