Laboratory of Bioinorganic Chemistry, Chemistry Department, University of Crete, 70013, Heraklion, Crete, Greece.
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, 11635, Athens, Greece.
ChemSusChem. 2021 Feb 5;14(3):961-970. doi: 10.1002/cssc.202002761. Epub 2020 Dec 18.
In this study, a highly efficient photocatalytic H production system is developed by employing porphyrins as photocatalysts. Palladium and platinum tetracarboxyporphyrins (PdTCP and PtTCP) are adsorbed or coadsorbed onto TiO nanoparticles (NPs), which act as the electron transport medium and as a scaffold that promotes the self-organization of the porphyrinoids. The self-organization of PdTCP and PtTCP, forming H- and J-aggregates, respectively, is the key element for H evolution, as in the absence of TiO NPs no catalytic activity is detected. Notably, J-aggregated PtTCPs are more efficient for H production than H-aggregated PdTCPs. In this approach, a single porphyrin, which self-organizes onto TiO NPs, acts as the light harvester and simultaneously as the catalyst, whereas TiO serves as the electron transport medium. Importantly, the concurrent adsorption of PdTCP and PtTCP onto TiO NPs results in the most efficient catalytic system, giving a turnover number of 22,733 and 30.2 mmol(H ) g(cat) .
在这项研究中，通过使用卟啉作为光催化剂，开发了一种高效的光催化制氢系统。钯和铂四羧基卟啉（PdTCP 和 PtTCP）被吸附或共吸附到 TiO2 纳米粒子（NPs）上，它们充当电子传输介质和促进卟啉自组织的支架。PdTCP 和 PtTCP 的自组织分别形成 H-和 J-聚集体，是 H 演化的关键因素，因为在没有 TiO2 NPs 的情况下，没有检测到催化活性。值得注意的是，J-聚集态的 PtTCP 比 H-聚集态的 PdTCP 更有利于 H 生产。在这种方法中，单个卟啉自组织到 TiO2 NPs 上，同时充当光捕获器和催化剂，而 TiO2 则充当电子传输介质。重要的是，PdTCP 和 PtTCP 同时吸附到 TiO2 NPs 上，产生了最有效的催化体系，给出了 22733 和 30.2mmol（H2）g（cat）-1 的周转数。
