Predicting the Mechanisms for H2O2 Activation and Phenol Oxidation Catalyzed by Modified Graphene-Based Systems Using Density Functional Theory,ACS Applied Materials & Interfaces

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Predicting the Mechanisms for H2O2 Activation and Phenol Oxidation Catalyzed by Modified Graphene-Based Systems Using Density Functional Theory
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2022-08-01 , DOI: 10.1021/acsami.2c08129
Bo Gong _{1,

2} , Calvin Ku ₁ , Han-Qing Yu ₂ , Patrick H-L Sit ₁

Affiliation

The heterogeneous Fenton-like reaction on metal-free graphene-based catalysts attracts great attention. However, a systematic and comprehensive understanding of the mechanisms for H₂O₂ activation and pollutant oxidation is still lacking. In this study, the heterogeneous Fenton-like mechanisms on doped and oxygen-containing graphene are investigated using density functional theory. The H₂O₂ tends to form a surface oxygen and a water molecule on the doped graphene. For the oxygen-containing graphene-based systems, relative to the groups in the basal plane, the separated groups on the edge including hydroxyl, carbonyl, and carboxyl readily activate H₂O₂ to hydroxyls. However, when the groups are close to each other, more additional side reactions might occur upon H₂O₂ adsorption, which may inhibit catalyst retrieval. Phenol is selected as a model pollutant to study its oxidation reaction with the adsorbed oxygen formed from the dissociated H₂O₂. The thermodynamics of the reactions depends significantly on the co-adsorption strengths over different catalysts. Our work provides key fundamental insights into the catalytic performance of various modified graphene-based systems, which could guide the future design and applications of heterogeneous Fenton reactions.

中文翻译：

使用密度泛函理论预测改性石墨烯基系统催化的 H2O2 活化和苯酚氧化机理

无金属石墨烯基催化剂上的非均相类芬顿反应引起了极大的关注。然而，仍然缺乏对H ₂ O ₂活化和污染物氧化机制的系统和全面了解。在这项研究中，使用密度泛函理论研究了掺杂和含氧石墨烯上的异质类芬顿机制。H ₂ O ₂倾向于在掺杂的石墨烯上形成表面氧和水分子。对于基于含氧石墨烯的体系，相对于基面中的基团，边缘上的分离基团包括羟基、羰基和羧基容易活化H ₂ O ₂为羟基。然而，当基团彼此靠近时，吸附H ₂ O ₂时可能会发生更多的附加副反应，这可能会抑制催化剂的回收。选择苯酚作为模型污染物，研究其与解离的H ₂ O ₂形成的吸附氧的氧化反应。反应的热力学很大程度上取决于不同催化剂的共吸附强度。我们的工作为各种改性石墨烯基系统的催化性能提供了关键的基本见解，这可以指导非均相芬顿反应的未来设计和应用。

更新日期：2022-08-01

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