Interplay between the Oxygen Reduction Reaction and Atom Transfer Radical Polymerization with Molecular Cu-Based Catalysts in Water

ACS Catalysis, vol. 15, pp. 14548–14563

Abstract

Determining the relationships between the catalyst structures of Cu-based molecular complexes and their performances in the oxygen reduction reaction (ORR), hydrogen peroxide reduction reaction (HPRR), and electrochemically mediated Atom Transfer Radical Polymerization ( e ATRP) is crucial for advancing radical polymerization in aerobic environments. Hence, Cu/tris(2-pyridylmethyl) amine (TMPA) was compared with Cu catalysts with TMPA ligands containing electron-donating para -substituents for aqueous ORR/HPRR catalysis and ATRP. Para -substitution decreased the ORR and HPRR activities, thereby reducing the O 2 consumption compared to that of Cu/TMPA. Para -substituted TMPA catalysts were suitable for acrylate polymerization, with M w / M n < 1.3, whereas the reaction rates of methacrylates were too high, leading to polymethacrylates with high M w / M n . Our results show that ORR/HPRR and ATRP are competitive, intertwined processes in aerobic water, with reactivities diverging upon the introduction of electron-donating para -substituents. These findings will facilitate future efforts to optimize Cu-based molecular catalysts by tuning their ligand structures to improve the performance of both ATRP and ORR/HPRR.

Authors 5

1. Phebe H. van Langevelde Aachen Leiden Institute of Chemistry

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry

   Leiden University

2. Katarina Ležaić Aachen Leiden Institute of Chemistry

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry

   Leiden University

3. Jorge F. J. Coelho

   Instituto Pedro Nunes · University of Coimbra

   Affiliation as printed

   CEMMPRE, ARISE, Department of Chemical Engineering, University of Coimbra, Rua Sílvio Lima, Pólo II, 3030-790 Coimbra, Portugal

   IPN, Instituto Pedro Nunes, Associação para a Inovação e Desenvolvimento em Ciência e Tecnologia, Rua Pedro Nunes, 3030-199 Coimbra, Portugal

4. Dennis G. H. Hetterscheid corresponding Aachen Leiden Institute of Chemistry

   Leiden University

   Affiliation as printed

   Leiden Institute of Chemistry

   Leiden University

5. Francesco De Bon corresponding

   University of Coimbra

   Affiliation as printed

   CEMMPRE, ARISE, Department of Chemical Engineering, University of Coimbra, Rua Sílvio Lima, Pólo II, 3030-790 Coimbra, Portugal