Bridging Atom Engineering for Low-Temperature Oxygen Activation in a Robust Metal-Organic Framework

Area of Science:

• Materials Science
• Catalysis
• Chemical Engineering

Background:

• Designing efficient catalysts for energy-intensive reactions requires atomic-level control of active sites.
• Competitive adsorption of reactants on catalytic sites complicates catalyst optimization for oxidation reactions.

Purpose of the Study:

• To engineer cobalt-based metal-organic framework (MOF) catalysts for enhanced oxygen activation.
• To investigate the impact of modifying the local coordination environment of metal centers on catalytic performance.

Main Methods:

• Synthesis of a robust metal-organic framework with tailored cobalt active sites.
• Substitution of bridging atoms (-Cl to -OH) to modify the local electronic structure.
• Comprehensive characterization techniques to analyze electronic structure, reactant adsorption, and intermediate formation.

Main Results:

• The -OH substitution drastically altered the electronic structure of cobalt centers and reactant adsorption behavior.
• The modified MOF catalyst exhibited exceptional low-temperature activity for carbon monoxide (CO) oxidation.
• Achieved T25 (35°C) and T100 (150°C) for CO oxidation, surpassing existing MOF catalysts and rivaling noble metals.

Conclusions:

• Atomic-level modification of the metal center's local environment in MOFs is a viable strategy for catalyst design.
• The developed MOF catalyst demonstrates high efficiency for oxygen activation and CO oxidation.
• This study provides a framework for designing advanced catalysts for efficient oxidation reactions.