Department of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea.
Dalton Trans. 2019 Jan 15;48(3):779-798. doi: 10.1039/c8dt04341h.
The kinetics and mechanisms of thermal and photochemical oxidation of water with homogeneous and heterogeneous catalysts, including conversion from homogeneous to heterogeneous catalysts in the course of water oxidation, are discussed in this review article. Molecular and homogeneous catalysts have the advantage to clarify the catalytic mechanisms by detecting active intermediates in catalytic water oxidation. On the other hand, heterogeneous nanoparticle catalysts have advantages for practical applications due to high catalytic activity, robustness and easier separation of catalysts by filtration as compared with molecular homogeneous precursors. Ligand oxidation of homogeneous catalysts sometimes results in the dissociation of ligands to form nanoparticles, which act as much more efficient catalysts for water oxidation. Since it is quite difficult to identify active intermediates on the heterogeneous catalyst surface, the mechanism of water oxidation has hardly been clarified under heterogeneous catalytic conditions. This review focuses on the kinetics and mechanisms of catalytic water oxidation with homogeneous catalysts, which may be converted to heterogeneous nanoparticle catalysts depending on various reaction conditions.
本文讨论了均相和多相催化剂作用下水的热和光化学氧化动力学和反应机理，包括水氧化过程中由均相催化剂向多相催化剂的转化。分子均相催化剂的优势在于可以通过检测催化水中氧化反应的活性中间体来阐明催化机制。另一方面，与分子均相前体相比，多相纳米颗粒催化剂由于具有高催化活性、稳定性和更容易通过过滤分离催化剂等优点，在实际应用中具有优势。均相催化剂的配体氧化有时会导致配体的解离形成纳米颗粒，这些纳米颗粒作为水氧化更有效的催化剂。由于在多相催化剂表面上很难识别活性中间体，因此在多相催化条件下，水氧化的反应机理几乎没有得到阐明。本综述重点介绍了均相催化剂作用下水的催化氧化动力学和反应机理，根据不同的反应条件，这些催化剂可能会转化为多相纳米颗粒催化剂。
