Crystallinity Modulation and Microenvironment Engineering Synergistically Manipulate ROS Generation on Ni Single-Atom Photocatalysts

The microenvironment modulation of metal-based catalysis sites plays a critical role in single-atom photocatalysis, and remains a grand challenge yet. Herein, the single-atom Ni anchored crystalline carbon nitride (Ni/CCN) nanowire arrays are reported. The obtained Ni/CCN nanowire arrays exhibit an impressive photocatalytic activity (>96% degradation of pharmaceuticals and personal care products (PPCPs) in only 5 min) and photocatalytic rate (maximum 0.5941 min(-1)) with only clean solar energy input. The Ni/CCN catalyst attached on microfiltration membrane in the continuous flow experiments exhibits >90% PPCPs degradation efficiency over 10 h, demonstrating the ultrahigh activity and long-term operation of the Ni/CCN catalysts. The results of electron spin resonance analysis, probe experiment and theoretical calculations demonstrate that the promoted generation of reactive oxygen species (ROS) highly relies on the crystallinity regulation and microenvironment engineering of active metal sites, which are consequently utilized to trigger the rapid degradation of PPCPs. The introduced Ni-N-4 moiety disrupts the uniform distribution of delocalized electrons and precisely tunes the electronic distribution of the microenvironment in CCN, providing an electron-rich region coupled with strong electron transfer effect between Ni and adsorbed O, thus optimizing the crucial step for molecular oxygen activation. This work offers a new idea of photocatalysis from theoretical design towards broad applications through the perspective about modulating microenvironment of active metal sites and optimizing intrinsic electronic properties.