From Single-Atom to Dual-Atom: A Universal Principle for the Rational Design of Heterogeneous Fenton-like Catalysts

Area of Science:

• Environmental Chemistry
• Materials Science
• Catalysis

Background:

• Developing efficient heterogeneous Fenton-like catalysts is crucial for advanced oxidation processes to remove organic micropollutants.
• A general design principle for highly efficient catalysts is currently lacking.

Purpose of the Study:

• To systematically explore single-atom and dual-atom transition metal/nitrogen/carbon (TM/N/C) catalysts for hydrogen peroxide (H2O2) dissociation.
• To establish a guiding principle for designing efficient heterogeneous Fenton-like catalysts.

Main Methods:

• Utilized high-throughput density functional theory and machine learning to screen 16 single-atom and 272 dual-atom TM/N/C catalysts.
• Investigated the H2O2 dissociation mechanism and correlated catalyst properties with catalytic activity.

Main Results:

• Identified a volcano-type relationship between catalytic activity and hydroxyl radical (•OH) adsorption energy for single-atom TM/N/C catalysts, with optimal adsorption energies between -3.11 and -2.20 eV.
• Discovered energetic, electronic, and structural descriptors correlating intrinsic catalyst properties with activity.
• Screened two dual-atom catalysts, CoCu/N/C and CoRu/N/C, exhibiting superior activity due to synergistic effects.

Conclusions:

• The study presents a novel understanding of H2O2 dissociation on TM/N/C catalysts.
• The identified volcano relationship and descriptors provide a conceptual framework for structure-oriented catalyst design.
• This work inspires the development of more efficient catalysts for advanced oxidation processes.