金属酞菁应用于两电子氧还原电催化的研究

两电子氧还原反应（2e^- ORR）可以提供一种分散式和清洁型的过氧化氢（H₂O₂）生产途径。电催化剂对这一重要反应的选择性与活性起到了至关重要的作用。发展并优化性能描述符有助于指导电催化剂的理性设计。然而，目前对性能描述符的认识仍然不足，高性能非贵金属电催化剂的发展也面临挑战。本文结合密度泛函理论计算和电化学测试，研究了一系列金属酞菁（MPcs，M = Co、Ni、Zn、Cu、Mn）在2e^- ORR中的催化性能。通过对反应自由能图的能量变化分析，提出*O和*OOH中间体的吸附能之差（ΔG_*O-ΔG_*OOH）和*H₂O₂中间体的吸附能（ΔG_*H2O2）可以作为选择性描述符，并在实验中得到验证。ΔG_*O-ΔG_*OOH或ΔG_*H2O2的值越正，则分别说明O-O键的断裂或H₂O₂的再吸附越难，越有利于选择性的提高。MPc分子锚定在碳纳米管上形成的单分子分散电催化剂（MDE）在旋转电极上具有比聚集分子更好的催化性能，其实验结果与理论计算也更吻合。其中，发现了CoPc MDE有更好的2e^-活性，而ZnPc MDE有更好的选择性。增加催化层的疏水性可以提升ΔG_*H2O2从而使选择性提高。在气体扩散电极中，ZnPc MDE和CoPc MDE均在较高的H₂O₂生产速率下具有低过电位、高选择性和良好的稳定性。本研究不仅发展了高效的MPc基2e^- ORR催化剂，还揭示了选择性描述符，为非贵金属电催化剂的理性设计提供了重要参考。

The  oxygen reduction reaction (  ORR) provides an appealing pathway to produce hydrogen peroxide (H₂O₂) in a decentralized and cleaner approach. Electrocatalysts play an important role in determining the selectivity and activity of this important reaction. Developing and optimizing performance descriptors is helpful to guide the rational design of electrocatalysts. However, the current understanding of performance descriptors is insufficient, and it is still challenging to develop high-performance noble-metal-free electrocatalysts. In this thesis, the catalytic performances of a series of metal phthalocyanines (MPcs, M = Co, Ni, Zn, Cu, Mn) for  ORR are studied by combining density functional theory calculations with electrochemical tests. By analyzing the energy changes of free energy profiles, the difference in the adsorption energy of *O and *OOH intermediates (ΔG_*O-ΔG_*OOH) and the adsorption energy of *H₂O₂ intermediate (ΔG_*H2O2) are proposed to be selectivity descriptors, which are confirmed by experiments. The value of  ΔG_*O-ΔG_*OOH or ΔG_*H2O2 becomes more positive, the O-O bond breaking or H₂O₂ adsorption is more difficult respectively, leading to higher selectivity. Molecularly dispersed electrocatalysts (MDEs) with MPcs anchored on carbon nanotubes exhibit better performances than those of aggregated molecules when tested on rotating electrodes. The experimental data of MDEs also match the theoretical calculation result better. Among them, CoPc MDE shows higher  activity, while ZnPc MDE shows higher selectivity. Increasing the hydrophobicity of the catalytic layer can increase ΔG_*H2O2 , leading to the improvement of selectivity. In the gas diffusion electrode measurements, both ZnPc MDE and CoPc MDE exhibit low overpotential, high selectivity, and good stability at high H₂O₂ production rates. This study not only develops efficient MPc-based  ORR catalysts, but also reveals selectivity descriptors, and provides guidelines for rational design of noble-metal-free electrocatalysts.

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