Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznanskiego 8, 61-614, Poznan, Poland.
Sci Rep. 2021 Apr 12;11(1):7977. doi: 10.1038/s41598-021-86880-1.
Graphene-based nanohybrids are good candidates for various applications. However, graphene exhibits some unwanted features such as low solubility in an aqueous solution or tendency to aggregate, limiting its potential applications. On the contrary, its derivatives, such as graphene oxide (GO) and reduced graphene oxide (RGO), have excellent properties and can be easily produced in large quantities. GO/RGO nanohybrids with porphyrins were shown to possess great potential in the field of photocatalytic hydrogen production, pollutant photodegradation, optical sensing, or drug delivery. Despite the rapid progress in experimental research on the porphyrin-graphene hybrids some fundamental questions about the structures and the interaction between components in these systems still remain open. In this work, we combine detailed experimental and theoretical studies to investigate the nature of the interaction between the GO/RGO and two metal-free porphyrins 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) and 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin (TPPH)]. The two porphyrins form stable nanohybrids with GO/RGO support, although both porphyrins exhibited a slightly higher affinity to RGO. We validated finite, Lerf-Klinowski-type (Lerf et al. in J Phys Chem B 102:4477, 1998) structural models of GO ([Formula: see text]) and RGO ([Formula: see text]) and successfully used them in ab initio absorption spectra simulations to track back the origin of experimentally observed spectral features. We also investigated the nature of low-lying excited states with high-level wavefunction-based methods and shown that states' density becomes denser upon nanohybrid formation. The studied nanohybrids are non-emissive, and our study suggests that this is due to excited states that gain significant charge-transfer character. The presented efficient simulation protocol may ease the properties screening of new GO/RGO-nanohybrids.
基于石墨烯的纳米杂化物是各种应用的良好候选材料。然而，石墨烯表现出一些不理想的特性，例如在水溶液中的低溶解度或倾向于聚集，限制了其潜在应用。相比之下，其衍生物，如氧化石墨烯（GO）和还原氧化石墨烯（RGO），具有优异的性能，并且可以大量生产。研究表明，具有卟啉的 GO/RGO 纳米杂化物在光催化制氢、污染物光降解、光学传感或药物输送等领域具有巨大潜力。尽管在卟啉-石墨烯杂化物的实验研究方面取得了快速进展，但这些系统中组件之间的结构和相互作用的一些基本问题仍然存在。在这项工作中，我们结合详细的实验和理论研究，研究了 GO/RGO 与两种无金属卟啉 5,10,15,20-四（4-氨基苯基）卟啉（TAPP）和 5,10,15,20-四（4-羟基苯基）卟啉（TPPH）之间相互作用的本质。这两种卟啉与 GO/RGO 载体形成稳定的纳米杂化物，尽管两种卟啉对 RGO 的亲和力稍高。我们验证了有限的 Lerf-Klinowski 型（Lerf 等人，在 J Phys Chem B 102:4477, 1998 年）GO ([Formula: see text])和 RGO ([Formula: see text])的结构模型，并成功地将它们用于从头算吸收光谱模拟中，以追溯实验观察到的光谱特征的起源。我们还使用基于波函数的高精度方法研究了低能激发态的性质，并表明在形成纳米杂化物后，态密度变得更加密集。所研究的纳米杂化物是非发光的，我们的研究表明，这是由于激发态具有显著的电荷转移特性。所提出的高效模拟方案可能会简化新的 GO/RGO-纳米杂化物的性质筛选。
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