单原子催化剂Ti/Ti3C2O2催化氧化甲醛的密度泛函理论研究

引用本文: 周君慧, 刘冠兰, 姜全国, 赵伟娜, 敖志敏, 安太成. 单原子催化剂Ti/Ti₃C₂O₂催化氧化甲醛的密度泛函理论研究[J]. 催化学报, 2020, 41(10): 1633-1644. doi: 10.1016/S1872-2067(20)63571-9 shu

Citation: Junhui Zhou, Guanlan Liu, Quanguo Jiang, Weina Zhao, Zhimin Ao, Taicheng An. Density functional theory calculations on single atomic catalysis: Ti-decorated Ti₃C₂O₂ monolayer (MXene) for HCHO oxidation[J]. Chinese Journal of Catalysis, 2020, 41(10): 1633-1644. doi: 10.1016/S1872-2067(20)63571-9 shu

单原子催化剂Ti/Ti₃C₂O₂催化氧化甲醛的密度泛函理论研究

a 广东工业大学环境健康与污染控制研究院, 环境科学与工程学院, 广东省环境催化与健康风险控制重点实验室, 广东广州 510006;
b 河海大学力学与材料学院, 江苏南京 211100
基金项目:
国家自然科学基金（21777033，21607029，41425015）；广东省科技计划（2017B020216003）；广东省教育厅创新团队项目（2017KCXTD012）.

摘要: 甲醛是一种比较常见的室内污染物，长期接触甲醛会危害人体健康.如何在低温条件下有效去除低浓度甲醛仍然是当前具有挑战性的研究课题.本文采用第一性原理计算方法研究了甲醛分子在单原子催化剂（Ti原子修饰的单层MXene-Ti₃C₂O₂）表面上的吸附和催化氧化性能.结果表明，Ti原子在Ti₃C₂O₂表面的结合能和扩散能分别为-8.36和1.66eV，说明Ti能够以单原子形式稳定分散在Ti₃C₂O₂表面，而不会产生团簇现象.为了研究甲醛和氧气分子在Ti/Ti₃C₂O₂上的吸附机理，我们计算了分波态密度（PDOS），Mulliken电荷分析以及分子轨道.结果表明，Ti原子修饰改变了Ti₃C₂O₂表面上的电荷分布，甲醛分子和氧气分子都能接受自Ti原子处转移而来的电子成为电子受体，增强了吸附质和Ti/Ti₃C₂O₂之间的相互作用，从而加强了吸附能力.
此外，为了研究甲醛分子在Ti/Ti₃C₂O₂上的催化氧化机理，我们考虑了Langmuir-Hinshelwood（LH）和Eley-Rideal（ER）两种机理.结果表明，无论是从动力学还是热力学角度，ER机理是一种更为理想的催化氧化甲醛的方式，甲醛分子在已经被氧气活化的Ti/Ti₃C₂O₂上能够自动解离成CO分子，而两个H原子则和活化的O原子形成两个*OH基团，并且释放4.05eV的热量，从而有助于克服后续反应所要跨越的能垒（1.04eV）.而从*OH基团到CO分子的电荷转移不仅能够促进*OH基团的活化，而且也为下一步的水分子的形成也提供了重要作用.综上所述，甲醛可以很容易地在单原子催化剂Ti/Ti₃C₂O₂上被氧化.综上，本文为开发高效去除甲醛的非贵金属催化剂以及扩大MXene材料应用范围提供重要指导.

关键词:

English

Density functional theory calculations on single atomic catalysis: Ti-decorated Ti₃C₂O₂ monolayer (MXene) for HCHO oxidation

a Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Guangzhou Key Laboratory Environmental Catalysis and Pollution Control, School of Environmental Science and Engineering, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou 510006, Guangdong, China;
b The College of Mechanics and Materials, Hohai University, Nanjing 211100, Jiangsu, China
Received Date: 21 February 2020
Revised Date: 23 March 2020
Fund Project:
This work was supported by National Natural Science Foundation of China (21777033, 21607029, 41425015), Science and Technology Planning Project of Guangdong Province (2017B020216003), and The Innovation Team Project of Guangdong Provincial Department of Education (2017KCXTD012).

Abstract: Formaldehyde (HCHO) is a common indoor pollutant, long-term exposure to HCHO may harm human health. Its efficient removal at mild conditions is still challenging. The catalytic oxidation of HCHO molecules on a single atomic catalyst, Ti-decorated Ti₃C₂O₂ (Ti/Ti₃C₂O₂) monolayer, is investigated by performing the first principles calculations in this work. It demonstrates that Ti atoms can be easily well dispersed at the form of single atom on Ti₃C₂O₂ monolayer without aggregation. For HCHO catalytic oxidation, both Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms are considered. The results show that the step of HCHO dissociative adsorption on Ti/Ti₃C₂O₂ with activated O₂ can release high energy of 4.05 eV based on the ER mechanism, which can help to overcome the energy barrier (1.04 eV) of the subsequent reaction steps. The charge transfer from *OH group to CO molecule (dissociated from HCHO) not only promotes ^*OH group activation but also plays an important role in the H₂O generation along the ER mechanism. Therefore, HCHO can be oxidized easily on Ti/Ti₃C₂O₂ monolayer, this work could provide significant guidance to develop effective non-noble metal catalysts for HCHO oxidation and broaden the applications of MXene-based materials.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

单原子催化剂Ti/Ti₃C₂O₂催化氧化甲醛的密度泛函理论研究

English

Density functional theory calculations on single atomic catalysis: Ti-decorated Ti₃C₂O₂ monolayer (MXene) for HCHO oxidation

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