Revealing the structure-activity relationship of Pt1/CeO2 with 17O solid-state NMR spectroscopy and DFT calculations
Yujie Wen, Fang Wang, Jie Zhu, Qian Wen, Xiaoli Xia, Juan Wen, Changshun Deng, Jia‐Huan Du, Xiaokang Ke, Zhen Zhang, Hanxi Guan, Lei Nie, Meng Wang, Wenhua Hou, Wei Li, Weiping Tang, Weiping Ding, Junchao Chen, Luming Peng
Abstract
Single-atom catalysts (SACs) have attracted significant interest due to their exceptional and tunable performance, enabled by diverse coordination environments achieved through innovative synthetic strategies. However, various local structures of active sites pose significant challenges for precise characterization, a prerequisite for developing structure-activity relationships. Here, we combine 17O solid-state NMR spectroscopy and DFT calculations to elucidate the detailed structural information of Pt/CeO2 SACs and their catalytic behaviors. The NMR data reveal that single Pt atoms, dispersed from clusters with water vapor, exhibit a square planar geometry embedded in CeO2 (111) surface, distinct from the original clusters and other conventionally generated Pt single atoms. The square planar Pt/CeO2 SAC demonstrates improved CO oxidation performance compared to Pt/CeO2 SAC with octahedral coordination, due to moderately strong CO adsorption and low energy barriers. This approach can be extended to other oxide-supported SACs, enabling spatially resolved characterization and offering comprehensive insights into their structure-activity relationships. Properly characterising active sites in single atom catalysts is important for mechanistic understanding but remains difficult. Here the authors combine 17O solid-state NMR spectroscopy and DFT calculations to probe the structures of Pt/CeO2 single atom catalysts, gaining insights into their structure-activity relationships.