Atomic Layer Deposition-Assisted Surface-Selective Isotopic Labeling for the 17O Solid-State NMR Studies of Metal Oxide Surfaces

Junchao Chen; Xiao Liu; Li Shen; Kuizhi Chen; Yujie Wen; Yang Wang; Xiaoli Xia; Fang Wang; Jennifer S Gomez; Ivan Hung; Weiping Tang; Zhehong Gan; Jia-Huan Du; Rong Chen; Luming Peng

doi:10.1021/acs.jpclett.5c01138

Atomic Layer Deposition-Assisted Surface-Selective Isotopic Labeling for the ¹⁷O Solid-State NMR Studies of Metal Oxide Surfaces

J Phys Chem Lett. 2025 Jun 28:6907-6913. doi: 10.1021/acs.jpclett.5c01138. Online ahead of print.

Authors

Junchao Chen¹, Xiao Liu², Li Shen^{3

4}, Kuizhi Chen⁵, Yujie Wen³, Yang Wang³, Xiaoli Xia³, Fang Wang³, Jennifer S Gomez⁶, Ivan Hung⁷, Weiping Tang¹, Zhehong Gan⁷, Jia-Huan Du⁸, Rong Chen², Luming Peng^{3

9

10}

Affiliations

¹ School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
² State Key Laboratory of Digital Manufacturing Equipment and Technology, School of Mechanical Science and Engineering, School of Optical and Electronic Information, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan 430074, China.
³ Key Laboratory of Mesoscopic Chemistry of MOE and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, 163 Xianlin Road, Nanjing 210023, China.
⁴ Guangling College, Yangzhou University, Yangzhou 225009, China.
⁵ State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, 2011-Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
⁶ Magnetic Resonance Research Center, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ Nijmegen, Netherlands.
⁷ National High Magnetic Field Laboratory (NHMFL), 1800 East Paul Dirac Drive, Tallahassee, Florida 32310, United States.
⁸ State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, China.
⁹ Jiangsu Key Laboratory of Vehicle Emissions Control, Nanjing University, Nanjing 210093, China.
¹⁰ Frontiers Science Center for Critical Earth Material Cycling (FSC-CEMaC), Nanjing University, Nanjing 210023, China.

PMID: 40580160
DOI: 10.1021/acs.jpclett.5c01138

Abstract

¹⁷O solid-state NMR spectroscopy is widely used to investigate metal oxide surfaces and is increasingly recognized for the unique insights into surface structures. Given the low natural abundance of the ¹⁷O nucleus (0.037%), ¹⁷O surface-selective isotopic labeling is commonly employed in relevant studies. Conventional thermal treatment (CTT)-labeling methods rely on rapid ¹⁷O/¹⁶O exchange may yield insufficient labeling on less reactive surfaces. Our approach uses atomic layer deposition (ALD) epitaxial growth to directly deposit ¹⁷O onto metal oxide surfaces regardless of surface reactivity. This method minimizes the formation of excessive surface hydroxyl groups, reducing overlapping NMR signals and enabling better ¹⁷O NMR identification of hydroxyl groups, as observed in Al₂O₃. Moreover, heteronuclear ²⁷Al{¹⁷O} J-HMQC NMR analysis reveals that the CTT method creates more correlations between penta-coordinated Al sites and hydroxyl groups in Al₂O₃ compared to ALD, indicating that the labeling techniques vary in their effectiveness at different surface sites.