The heterogeneous photo-Fenton-like process promises outstanding water decontamination, but the low H2O2 utilization stemming from an insufficient supply of energetic electrons remains a bottleneck. Here, we propose an ingenious design to overcome this challenge by creating electron-rich Cu(I) sites and defective structures in asymmetric copper silicate nanotubes (CSNs) to achieve full-spectrum-driven photo-Fenton-like catalysis. The intrinsic electric field and oxygen vacancy synergistically accelerate the directional migration of the photogenerated electrons to continuously regenerate Cu(I) for H2O2 activation. Simultaneously, the strong electron delocalization of the Cu(I) sites reduces the electron density of the adjacent bridging H sites, greatly improving the H2O2 adsorption. As a result, the utilization of H2O2 is significantly improved, realizing the superior and long-lasting CSN-catalyzed Fenton-like reaction upon full-spectrum irradiation.

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.