Unraveling Valence Electron Number Dependent Excitonic Effects over M1-N3C1 Sites in Single-Atom Catalysts.

Excitonic effects significantly influence the selective generation of reactive oxygen species and photothermal conversion efficiency in photocatalytic reactions; however, the intrinsic factors governing excitonic effects remain elusive. Herein, a series of single-atom catalysts with well-defined M1-N3C1 (M = Mn, Fe, Co, and Ni) active sites are designed and synthesized to investigate the structure-activity relationship between photocatalytic materials and excitonic effects. Comprehensive characterization and theoretical calculations unveil that excitonic effects are positively correlated with the number of valence electrons in single metal atoms. The single Mn atom with 5.93 valence electrons exhibits the weakest excitonic effects, which dominate superoxide radical (O2•-) generation through charge transfer and enhance photothermal conversion efficiency. Conversely, the single Ni atom with 9.27 valence electrons exhibits the strongest excitonic effects, dominating singlet oxygen (1O2) generation via energy transfer while suppressing photothermal conversion efficiency. Based on the valence electron number dependent excitonic effects, a reaction environment with hyperthermia and abundant cytotoxic O2•- is designed, achieving efficient and stable water disinfection. This work reveals single metal atom dependent excitonic effects and presents an atomic-level methodology for catalytic application targeted reaction environment tailoring.

Solar-driven strongly coupled plasmonic Au nanoarrays on mesoporous silica nanodisks enable selective fungal and bacterial inactivation in well water.

Well water is an important water source in isolated rural areas but easily suffers from microbial contamination. Herein, we anchored periodic Au nanoarrays on mesoporous silica nanodisks (Au-MSN) to fabricate a solar-driven nano-stove for well water disinfection. The solar/Au-MSN process completely inactivated 3.98, 6.55, 7.11 log10 cfu/mL, and 3.37 log10 pfu/mL of Aspergillus niger spores, Escherichia coli, chlorine-resistant Spingopyxis sp. BM1-1, and bacteriophage MS2 within 5 min, respectively. Moreover, the complete inactivation of various microorganisms (even at a viable but nonculturable state) was achieved in the flow-through reactor under natural solar light in real well water matrixes. Thorough characterizations and theoretical simulations verified that the densely anchoring strategy of Au-MSN's nanoarray worked on broadband absorption via the photon confinement effect, and trace amounts of Au can induce strong electromagnetic fields and collective localized heating. The resulting surge of 1O2 and heat synergically destroyed membranes, dysfunction cellular self-defense and metabolic system, induced intracellular oxidative stress, and ultimately inactivated microorganisms. Additionally, the 1O2-dominated oxidation and cell adhesion facilitated the selective disinfection in real well water matrixes. This study provides a cost-effective and practical solution for efficient well water disinfection, which assists isolated rural areas in getting safe drinking water.

A modified flower pollen-based photothermocatalytic process for enhanced solar water disinfection: Photoelectric effect and bactericidal mechanisms.

Solar disinfection (SODIS) is regarded as an affordable and effective point-of-use (POU) water disinfection treatment urgently needed in rural developing world. This work developed an enhanced SODIS scheme that utilized a novel flower pollen-based catalyst (Te-TRP). The bench-scale experiments demonstrated 100% photothermocatalytic inactivation of approximately 7-log E. coli K-12, Spingopyxis sp. BM1-1, or S. aureus bacterium by Te-TRP within 40-60 min. Moving toward practical device design, we constructed a flow-through reactor and demonstrated the outstanding water disinfection performance of Te-TRP. The in-depth mechanistic study revealed the synergetic effect between photocatalysis and photothermal conversion and identified the bacterial inactivation pathway. 1O2 and ·O2¯ were verified to be the dominant reactive oxygen species involved in the bacterial inactivation. The damage to bacterial cells caused by photothermocatalytic reactions was systematically investigated, demonstrating the cell membrane destruction, the loss of enzyme activity, the increased cell membrane permeability, and the complete inactivation of bacteria without the viable but nonculturable state cells. This work not only affords a facile approach to preparing biomaterial-based catalysts capable of efficient photothermocatalytic bacterial inactivation, but also proposes a prototype of POU water treatment, opening up an avenue for sustainable environmental remediation.