Decavanadate Coordination Polymers With Transition-Metal-BisTris Cations for Synergistic Atmospheric CO₂...

Area of Science:

• Materials Science
• Catalysis
• Green Chemistry

Background:

• Carbon dioxide (CO2) utilization via cycloaddition with epoxides to form cyclic carbonates is crucial for sustainable chemistry.
• Development of efficient, recyclable heterogeneous catalysts operating under mild conditions is essential for CO2 fixation.
• Decavanadate-based materials offer potential as robust catalytic platforms.

Purpose of the Study:

• To synthesize and characterize novel BisTris-modified decavanadate-based coordination polymers as heterogeneous catalysts.
• To evaluate the catalytic performance of these materials in the cycloaddition of CO2 with epoxides under mild conditions.
• To elucidate the cooperative catalytic mechanisms involving decavanadate anions, transition metals, and BisTris ligands.

Main Methods:

• Synthesis of five BisTris-modified decavanadate coordination polymers under mild acidic conditions.
• Structural characterization using single-crystal X-ray diffraction.
• Catalytic testing for CO2 cycloaddition with epichlorohydrin under 1 atm CO2 at 60°C, including recyclability and substrate scope studies.

Main Results:

• All synthesized catalysts exhibited >99% selectivity for cyclic carbonate formation.
• The zinc-containing catalyst (Compound 5) achieved the highest yield (98.2%) under mild conditions.
• Cooperative effects from vanadium Lewis acid sites, transition metal centers, and BisTris hydroxyl groups were confirmed.

Conclusions:

• BisTris-modified decavanadate coordination polymers are effective heterogeneous catalysts for CO2 cycloaddition.
• The modular design strategy allows for tuning catalytic activity and highlights the importance of cooperative interactions.
• The developed catalysts show high efficiency, recyclability, and broad epoxide tolerance for sustainable carbon utilization.