Copper nanoclusters-doped novel carrier with synergistic adsorption-catalytic active sites to enable high-performance dye removal

Enhancing the synergistic interplay between adsorption and catalytic oxidation to amplify Fenton-like effects remains a pivotal challenge in advancing water pollution remediation strategies. In this study, a suite of novel carriers (SH) composed of silica (SiO2) and hydroxyapatite (HAp) in different ratios were synthesized through an amalgamation of the sol-gel and co-precipitation techniques. Notably, various forms of copper (Cu) species, including Cu2+ ions and Cu nanoclusters (Cu NCs), could be stably incorporated onto the SH surface via meticulous loading and doping techniques. This approach has engendered a new class of Fenton-like catalysts (Cu NCs-SH1-5) characterized by robust acid-base tolerance stability and remarkable recyclability. Compared with the previously reported Cu NCs-HAp, this catalyst with lower Cu species content could achieve better performance in adsorbing and degrading dyes under the aid of hydrogen peroxide (H2O2). The catalyst's dual action sites, specifically the adsorption sites (SiOH, POH, slit pores) and catalytic centers (multivalent Cu species), had clear division of labor and collaborate with each other. Further, reactive oxygen species (ROS) identification and astute electrochemical testing have unveiled the mechanism underpinning the cooperative degradation of dyes by three types of ROS, spawned through electron transfer between the Fenton-like catalyst (Cu NCs-SH) and H2O2. From these insights, the mechanism of synergistic adsorption-catalytic removal was proposed.