Yang Changju, Wang Jia, Xia Xiaoli, Ding Liping, Wen Yujie, Zhao Taotao, Ke Xiaokang, Gong Xue-Qing, Wu Xin-Ping, Ding Weiping, Peng Luming
Key Laboratory of Mesoscopic Chemistry of Ministry of Education and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China.
J Phys Chem Lett. 2024 Aug 15;15(32):8218-8223. doi: 10.1021/acs.jpclett.4c01926. Epub 2024 Aug 5.
The impacts of subsurface species of catalysts on reaction processes are still under debate, largely due to a lack of characterization methods for distinguishing these species from the surface species and the bulk. By using O solid-state nuclear magnetic resonance (NMR) spectroscopy, which can distinguish subsurface oxygen ions in CeO (111) nanorods, we explore the effects of subsurface species of oxides in CO oxidation reactions. The intensities of the O NMR signals due to surface and subsurface oxygen ions decrease after the introduction of CO into CeO nanorods, with a more significant decrease observed for the latter, confirming the participation of subsurface oxygen species. Density functional theory calculations show that the reaction involves subsurface oxygen ions filling the surface oxygen vacancies created by the direct contact of surface oxygen with CO. This new approach can be extended to the study of the role of oxygen species in other catalytic reactions.
催化剂的次表面物种对反应过程的影响仍在争论中，这主要是由于缺乏将这些物种与表面物种及体相区分开来的表征方法。通过使用可以区分CeO(111)纳米棒中次表面氧离子的O 固态核磁共振(NMR)光谱，我们探究了氧化物的次表面物种在CO氧化反应中的作用。将CO引入CeO纳米棒后，由表面和次表面氧离子引起的O NMR信号强度降低，其中后者的降低更为显著，这证实了次表面氧物种的参与。密度泛函理论计算表明，该反应涉及次表面氧离子填充由表面氧与CO直接接触产生的表面氧空位。这种新方法可以扩展到研究氧物种在其他催化反应中的作用。
