Tang Tian, Zhao ShunZheng, Liu YunPeng, Tang XiaoLong, Sun Long, Ma YiMing, Zhu RongHui, Yi HongHong
Department of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China.
Department of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China.
J Hazard Mater. 2024 Dec 5;480:135839. doi: 10.1016/j.jhazmat.2024.135839. Epub 2024 Sep 15.
A precious metal catalyst with loaded Pt single atoms was prepared and used for the complete oxidation of CHO. Detailed results show that the T of the 1.5Pt SA/γ-AlO catalyst in the oxidation process of acetone is 250 °C, the TOF of Pt is 1.09 × 10 s, and the catalyst exhibits good stability. Characterization reveals that the high dispersion of Pt single atoms and strong interaction with the carrier improve the redox properties of the catalyst, enhancing the adsorption and dissociation capability of gaseous oxygen. DFT calculations show that after the introduction of Pt, the oxygen vacancy formation energy on the catalyst surface is reduced to 1.2 eV, and PDOS calculations prove that electrons on Pt atoms can be quickly transferred to O atoms, increasing the number of electrons on the σ * bond and promoting the escape of lattice oxygen. In addition, in situ DRIFTS and adsorption experiments indicate that the CHO oxidation process follows the Mars-van Krevelen reaction mechanism, and CH =C(CH)=O, O* (O), formate, acetate, and carbonate are considered as the main intermediate species and/or transients in the reaction process. Particularly, the activation rate of O and the cleavage of the -C-C- bond are the main rate-determining steps in the oxidation of CHO. This work will further enhance the study of the oxidation mechanism of oxygenated volatile organic pollutants over loaded noble metal catalysts.
制备了负载Pt单原子的贵金属催化剂并将其用于CHO的完全氧化。详细结果表明,1.5Pt SA/γ-AlO催化剂在丙酮氧化过程中的T为250℃,Pt的TOF为1.09×10 s,且该催化剂表现出良好的稳定性。表征显示,Pt单原子的高分散性以及与载体的强相互作用改善了催化剂的氧化还原性能,增强了气态氧的吸附和解离能力。DFT计算表明,引入Pt后,催化剂表面的氧空位形成能降低至1.2 eV,PDOS计算证明Pt原子上的电子可快速转移至O原子,增加了σ 键上的电子数并促进了晶格氧的逸出。此外,原位DRIFTS和吸附实验表明,CHO氧化过程遵循Mars-van Krevelen反应机理,CH =C(CH)=O、O (O)、甲酸盐、乙酸盐和碳酸盐被认为是反应过程中的主要中间物种和/或过渡态。特别地,O的活化速率和-C-C-键的断裂是CHO氧化过程中的主要速率决定步骤。这项工作将进一步加强对负载型贵金属催化剂上含氧挥发性有机污染物氧化机理的研究。