DFT-Based Investigation of Pd-Modified WO3/Porous Silicon Composites for NO2 Gas Sensors: Enhanced Synergistic Effect and High-Performance Sensing

Pd-WO3 coatings on porous silicon (PSi) substrates are engineered to enhance interfacial charge transfer and surface reactivity through atomic-scale structural tailoring. This study combines first-principles calculations and experimental characterization to elucidate how Pd nanoparticles (NPs) optimize the coating’s electronic structure and environmental stability. The hierarchical PSi framework with uniform nanopores (200–500 nm) serves as a robust substrate for WO3 nanorod growth (50–100 nm diameter), while Pd decoration (15%–20% surface coverage) strengthens Pd–O–W interfacial bonds, amplifying electron density at the Fermi level by 2.22-fold. Systematic computational analysis reveals that Pd-induced d-p orbital hybridization near the Fermi level (−2 to +1 eV) enhances charge delocalization, optimizing interfacial charge transfer. Experimentally, these modifications enhance the coating’s response to environmental degradation, showing less than 3% performance decay over 30 days under cyclic humidity (45 ± 3% RH). Although designed for gas sensing, the coating’s high surface-to-volume ratio and delocalized charge transport channels demonstrate broader applicability in catalytic and high-stress environments. This work provides a paradigm for designing multifunctional coatings through synergistic interface engineering.