Department of Chemistry, University of North Carolina Chapel Hill , Chapel Hill, North Carolina 27599, United States.
Department of Chemistry and Biochemistry, Florida International University , 11200 SW Eighth Street, Miami, Florida 33199, United States.
J Am Chem Soc. 2018 Jan 17;140(2):719-726. doi: 10.1021/jacs.7b10809. Epub 2018 Jan 2.
Water oxidation is a critical step in artificial photosynthesis and provides the protons and electrons used in reduction reactions to make solar fuels. Significant advances have been made in the area of molecular water oxidation catalysts with a notable breakthrough in the development of Ru(II) complexes that use a planar "bda" ligand (bda is 2,2'-bipyridine-6,6'-dicarboxylate). These Ru(II)(bda) complexes show lower overpotentials for driving water oxidation making them ideal for light-driven applications with a suitable chromophore. Nevertheless, synthesis of heterogeneous Ru(II)(bda) complexes remains challenging. We discuss here a new "bottom-up" synthetic method for immobilizing these catalysts at the surface of a photoanode for use in a dye-sensitized photoelectrosynthesis cell (DSPEC). The procedure provides a basis for rapidly screening the role of ligand variations at the catalyst in order to understand the impact on device performance. The best results of a water-oxidation DSPEC photoanode based on this procedure reached 1.4 mA/cm at pH 7 in 0.1 M [POH]/[POH]solution with minimal loss in catalytic behavior over 30 min, and produced an incident photon to current efficiency (IPCE) of 24.8% at 440 nm.
水氧化是人工光合作用的关键步骤，为还原反应提供质子和电子，以制造太阳能燃料。在分子水氧化催化剂领域取得了重大进展，其中一个显著的突破是开发了使用平面“bda”配体（bda 是 2,2'-联吡啶-6,6'-二羧酸）的 Ru(II)配合物。这些 Ru(II)(bda)配合物在驱动水氧化方面表现出较低的过电势，使其成为具有合适发色团的光驱动应用的理想选择。然而，异相 Ru(II)(bda)配合物的合成仍然具有挑战性。我们在这里讨论了一种新的“自下而上”的合成方法，用于将这些催化剂固定在光阳极的表面，用于染料敏化光电化学电池（DSPEC）。该程序为快速筛选催化剂中配体变化的作用提供了基础，以便了解其对器件性能的影响。基于该程序的水氧化 DSPEC 光阳极的最佳结果是在 pH 7 的 0.1 M [POH]/[POH]溶液中达到 1.4 mA/cm，在 30 分钟内催化性能的最小损失，在 440nm 处产生的光电子电流效率（IPCE）为 24.8%。
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