Semiconductor Nanoporous Anodic Alumina Photonic Crystals as a Model Photoelectrocatalytic Platform for Solar Light‐Driven Reactions

In this study, nanoporous anodic alumina distributed‐Bragg reflectors (NAA–DBRs) functionalized with tungsten trioxide (WO 3 ) are used as prototype photoelectrocatalysts (PEC) for harnessing the slow photon effect to maximize photon‐to‐electron conversion efficiency under UV–visible–NIR illumination. NAA–DBR structures are structurally engineered by anodization, where their characteristic photonic stopband is precisely tuned along specific positions of the UV–visible spectrum. Subsequent atomic layer deposition is employed to coat the inner surface of these porous structures with WO 3 semiconductor layers. Upon the application of overpotential bias, these platforms reveal excellent electron–hole pair separation to boost photoelectrocatalytic reactions. Photoelectrochemical degradation of methylene blue is used as a model reaction to elucidate enhancements associated with structural and optoelectronic arrangements. Notably, precise spectral alignment between the photonic stopband's red edge and the absorbance band of methylene blue enhances the degradation performance through the slow photon effect. Applying an overpotential bias further improves the photodegradation performance through efficient charge separation. These systems outperform comparable structures in this model reaction, achieving a maximum kinetic rate of 13.7 ± 2.0 h −1 . The findings create new opportunities to develop high‐performing PEC technologies harnessing light–matter interactions.