Hoque Md Asmaul, Gil-Sepulcre Marcos, de Aguirre Adiran, Elemans Johannes A A W, Moonshiram Dooshaye, Matheu Roc, Shi Yuanyuan, Benet-Buchholz Jordi, Sala Xavier, Malfois Marc, Solano Eduardo, Lim Joohyun, Garzón-Manjón Alba, Scheu Christina, Lanza Mario, Maseras Feliu, Gimbert-Suriñach Carolina, Llobet Antoni
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona, Spain.
Institute for Molecules and Materials, Radboud University, Nijmegen, The Netherlands.
Nat Chem. 2020 Nov;12(11):1060-1066. doi: 10.1038/s41557-020-0548-7. Epub 2020 Sep 28.
Photoelectrochemical cells that utilize water as a source of electrons are one of the most attractive solutions for the replacement of fossil fuels by clean and sustainable solar fuels. To achieve this, heterogeneous water oxidation catalysis needs to be mastered and properly understood. The search continues for a catalyst that is stable at the surface of electro(photo)anodes and can efficiently perform this reaction at the desired neutral pH. Here, we show how oligomeric Ru complexes can be anchored on the surfaces of graphitic materials through CH-π interactions between the auxiliary ligands bonded to Ru and the hexagonal rings of the graphitic surfaces, providing control of their molecular coverage. These hybrid molecular materials behave as molecular electroanodes that catalyse water oxidation to dioxygen at pH 7 with high current densities. This strategy for the anchoring of molecular catalysts on graphitic surfaces can potentially be extended to other transition metals and other catalytic reactions.
利用水作为电子源的光电化学电池是用清洁且可持续的太阳能燃料替代化石燃料最具吸引力的解决方案之一。要实现这一点,需要掌握并正确理解多相水氧化催化。人们仍在寻找一种在电(光)阳极表面稳定且能在所需中性pH值下高效进行此反应的催化剂。在此,我们展示了如何通过与Ru键合的辅助配体和石墨表面的六元环之间的CH-π相互作用,将寡聚Ru配合物锚定在石墨材料表面,从而控制其分子覆盖率。这些混合分子材料表现为分子电阳极,在pH值为7时能以高电流密度催化水氧化成氧气。这种将分子催化剂锚定在石墨表面的策略有可能扩展到其他过渡金属和其他催化反应。