RESUMEN
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 (O2â¢-) 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 O2â¢- 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.
RESUMEN
Comprehensively understanding the interdependency between the orientated atomic array and intrinsic piezoelectricity in one-dimension (1D) tellurium (Te) crystals will greatly benefit their practical piezo-catalytic applications. Herein, we successfully synthesized the various 1D Te microneedles by precisely orientating the atomic growth orientation by tuning (100)/(110) planes ratios (Te-0.6, Te-0.3, Te-0.4) to reveal the secrets of piezoelectricity. Explicitly, the theoretical simulations and experimental results have solidly validated that the Te-0.6 microneedle grown along the [110] orientation possesses a stronger asymmetric distribution of Te atoms array causing the enhanced dipole moment and in-plane polarization, which boosts a higher transfer and separation efficiency of the electron and hole pairs and a higher piezoelectric potential under the same stress. Additionally, the orientated atomic array along the [110] has p antibonding states with a higher energy level, resulting in a higher CB potential and a broadened band gap. Meanwhile, it also has a much lower barrier toward the valid adsorption of H2O and O2 molecules over other orientations, effectively conducive to the production of reactive oxygen species (ROS) for the efficient piezo-catalytic sterilization. Therefore, this study not only broadens the fundamental perspectives in understanding the intrinsic mechanism of piezoelectricity in 1D Te crystals but also provides a candidate 1D Te microneedle for practical piezo-catalytic applications.
RESUMEN
In rural areas where low-temperature groundwater is used as a drinking water source, cost-effective sterilization techniques are needed to prevent groundwater consumers from the disease risks triggered by pathogenic microorganisms like Escherichia coli and fungal spores. In this study, micro/nano bubbles (MNBs) coupled with the tellurium (Te)-based catalysts were used to considerably enhance the solar disinfection (SODIS) efficiency while overcoming the intrinsic defects of SODIS, particularly in low-temperature. Sterilization tests showed that 6.5 log10 cfu/mL of E. coli K-12 and 4.0 log10 cfu/mL of Aspergillus niger spores were completely inactivated within 5 min while applying this novel process for disinfection of raw groundwater, even in low-temperature. The underlying mechanisms of the extraordinary sterilization efficiency were revealed through comprehensive characterization of the catalysts and the physiological changes of the microorganisms. The localized surface plasmon resonance (LSPR) effect of the Te catalysts was identified to take advantage of photothermal synergism to achieve cell death. The integration of MNBs with the facet-engineered Te catalysts improved the photothermal catalytic effect and extracellular electron transfer, which substantially strengthened disinfection efficiency. This study provides a targeted solution into microbial inactivation in groundwater and emphasizes a cost-effective groundwater sterilization process.