Spatially asymmetric catalyst design with electron-rich Cu sites to facilitate full-spectrum photo-Fenton-like catalysis

Heterogeneous photo-Fenton catalysis stands out as a promising advanced oxidation technology but is subject to slow reaction kinetics because the electron supply is insufficient to sustain the Fenton reaction. Here, we demonstrate an asymmetric-catalyst-based copper silicate nanotube (CSN) Janus design that simultaneously enables favorable full-spectrum solar absorption, H₂O₂ adsorption, and catalytic activity. The coordination asymmetry induces oxygen-vacancy-associated, electron-rich Cu(I) sites and an intrinsic electric field oriented from the Si-O to the Cu-O sublayer, synergistically driving the photoexcited electrons to compensate for the electron-donating capability of Cu sites, leading to remarkably enhanced H₂O₂ activation. The strong electron delocalization of Cu(I) sites reinforces the H₂O₂ adsorption on its adjacent bridging H sites. The energy barrier for H₂O₂ dissociation is vastly reduced (0.912 → 0.264 eV), boosting H₂O₂ utilization (54%, almost two times higher than that of conventional catalysts). The CSN-catalyzed photo-Fenton-like reaction attains long-lasting ·OH production, which affords exceptional performance for various types of organic pollutant elimination.