Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstraße 3, D-91058 Erlangen, Germany.
Phys Chem Chem Phys. 2018 Oct 3;20(38):24858-24868. doi: 10.1039/c8cp04873h.
Hybrid materials consisting of functional organic molecules on metal oxide nanomaterials are key components in emerging technologies, for example in energy conversion and molecular electronics. In this work, we present the results of a comparative study of carboxyl-functionalized porphyrins on different oxide nanomaterials. Specifically, we investigated the interaction of 5(3-carboxyphenyl)-10,15,20-triphenyl-21,23H-porphyrin (2H-3-MCTPP) and 5(4-carboxyphenyl)-10,15,20-triphenyl-21,23H-porphyrin (2H-4-MCTPP), on MgO, TiO2, and Co3O4 nanoparticles (NPs) using isothermal and temperature-programmed diffuse reflection infrared Fourier transform spectroscopy (DRIFTS). We show that both porphyrins bind to the NPs, yielding stable monolayer films consisting of tilted surface carboxylates. In all cases, anchoring through the carboxylic acid group suppresses self-metalation of the porphyrin unit. Upon annealing, all anchored porphyrin films undergo metalation. The position of the acid group has no major influence on the reactivity. The same is true for the nature of the metal oxide, suggesting that the observed behaviour is general for most anchored porphyrin films on oxide nanomaterials.
由功能有机分子在金属氧化物纳米材料上形成的杂化材料是新兴技术的关键组成部分，例如在能量转换和分子电子学中。在这项工作中，我们展示了对不同氧化物纳米材料上羧基功能化卟啉的比较研究结果。具体来说，我们研究了 5(3-羧基苯基)-10,15,20-三苯基-21,23H-卟啉（2H-3-MCTPP）和 5(4-羧基苯基)-10,15,20-三苯基-21,23H-卟啉（2H-4-MCTPP）在 MgO、TiO2 和 Co3O4 纳米粒子（NPs）上的相互作用，使用等温和程序升温漫反射红外傅里叶变换光谱（DRIFTS）。我们表明，两种卟啉都与 NPs 结合，生成由倾斜表面羧酸酯组成的稳定单层膜。在所有情况下，通过羧酸基团的锚定都抑制了卟啉单元的自金属化。退火后，所有固定的卟啉膜都经历了金属化。酸基团的位置对反应性没有重大影响。对于金属氧化物的性质也是如此，这表明所观察到的行为对于大多数氧化物纳米材料上的固定卟啉膜是普遍的。
