Li Shangkun, Zhang Zeyi, Marks Walker R, Huang Xinan, Chen Hang, Stoian Dragos C, Erni Rolf, Triana Carlos A, Patzke Greta R
Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057, Zurich, Switzerland.
Department of Chemistry, University of Basel, Mattenstrasse 24a, CH-4058, Basel, Switzerland.
Nat Commun. 2024 Sep 29;15(1):8432. doi: 10.1038/s41467-024-52514-z.
Exploration of efficient molecular water oxidation catalysts for long-term application remains a key challenge for the conversion of renewable energy sources into fuels. Cuboidal {CoO} complexes keep attracting interest as molecular water oxidation catalysts as they combine features of both heterogeneous and homogeneous catalysis with bio-inspired motifs. However, the application of many cluster-based catalysts for the oxygen evolution reaction still requires new stabilization strategies. Drawing inspiration from the stabilizing effects of natural polymers, we introduce a conductive polymer-hybrid approach to covalently immobilize {CoO} cubane oxo clusters as oxygen evolution catalysts. Polypyrrole is applied as an efficient p-type conducting polymer that promotes hole transfer during the oxygen evolution reaction, resulting in higher turnover frequency compared to the pristine {CoO} oxo cluster and heterogeneous Co-oxide benchmarks. The asymmetric coordination of {CoO} not only mitigates catalyst decomposition pathways, but also increases the catalytic efficiency by exposing a directed cofacial dihydroxide motif during catalysis.
探索适用于长期应用的高效分子水氧化催化剂仍然是将可再生能源转化为燃料的关键挑战。立方{CoO}配合物作为分子水氧化催化剂一直备受关注，因为它们结合了多相催化和均相催化的特点以及受生物启发的结构基序。然而，许多基于簇的催化剂在析氧反应中的应用仍需要新的稳定策略。受天然聚合物稳定作用的启发，我们引入了一种导电聚合物杂化方法，将{CoO}立方烷氧簇共价固定为析氧催化剂。聚吡咯被用作一种高效的p型导电聚合物，在析氧反应过程中促进空穴转移，与原始的{CoO}氧簇和多相氧化钴基准相比，具有更高的周转频率。{CoO}的不对称配位不仅减轻了催化剂的分解途径，还通过在催化过程中暴露定向的共面二羟基结构基序提高了催化效率。
