Max Planck Institute for Solid State Research , Heisenbergstrasse 1, 70569 Stuttgart, Germany.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, CONICET , Sucursal 4 Casilla de Correo 16, 1900 La Plata, Argentina.
J Am Chem Soc. 2016 Mar 23;138(11):3623-6. doi: 10.1021/jacs.5b10484. Epub 2016 Mar 10.
Developing efficient catalysts for electrolysis, in particular for the oxygen evolution in the anodic half cell reaction, is an important challenge in energy conversion technologies. By taking inspiration from the catalytic properties of single-atom catalysts and metallo-proteins, we exploit the potential of metal-organic networks as electrocatalysts in the oxygen evolution reaction (OER). A dramatic enhancement of the catalytic activity toward the production of oxygen by nearly 2 orders of magnitude is demonstrated for novel heterobimetallic organic catalysts compared to metallo-porphyrins. Using a supramolecular approach we deliberately place single iron and cobalt atoms in either of two different coordination environments and observe a highly nonlinear increase in the catalytic activity depending on the coordination spheres of Fe and Co. Catalysis sets in at about 300 mV overpotential with high turnover frequencies that outperform other metal-organic catalysts like the prototypical hangman porphyrins.
开发高效的催化剂用于电解，特别是用于阳极半反应中的氧气析出反应，是能源转换技术中的一个重要挑战。受单原子催化剂和金属蛋白酶的催化特性的启发，我们利用金属有机网络作为电催化剂在氧气析出反应（OER）中的潜力。与金属卟啉相比，新型杂双金属有机催化剂在氧气生成方面的催化活性提高了近两个数量级。通过超分子方法，我们有意将单个铁和钴原子置于两种不同的配位环境中，并观察到催化活性随 Fe 和 Co 的配位球高度非线性增加。在 300 mV 过电势下即可引发催化作用，具有高的转化频率，优于其他金属有机催化剂，如典型的绞刑吏卟啉。
