Highly efficient and robust molecular ruthenium catalysts for water oxidation
2012 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 109, no 39, 15584-15588 p.Article in journal (Refereed) Published
Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H-2 driven by solar radiation (H2O + h nu -> 1/2O(2) + H-2). The oxidation of water (H2O -> 1/2O(2) + 2H(+) + 2e(-)) provides protons and electrons for the production of dihydrogen (2H(+) + 2e(-) -> H-2), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes [Ru(bda)L-2] (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze Ce-IV-driven [Ce-IV = Ce(NH4)(2()NO3)(6)] water oxidation with high oxygen production rates up to 286 s(-1) and high turnover numbers up to 55,400.
Place, publisher, year, edition, pages
2012. Vol. 109, no 39, 15584-15588 p.
catalysis, density function theory, seven coordination, photosystem II, solar fuels
IdentifiersURN: urn:nbn:se:kth:diva-104377DOI: 10.1073/pnas.1118347109ISI: 000309604500019ScopusID: 2-s2.0-84866844020OAI: oai:DiVA.org:kth-104377DiVA: diva2:564798
FunderSwedish Research CouncilKnut and Alice Wallenberg Foundation
QC 201211052012-11-052012-11-012012-11-05Bibliographically approved