Surface differences of oxide nanocrystals determined by geometry and exogenously coordinated water molecules

Junchao Chen; Xin-Ping Wu; Michael A Hope; Zhiye Lin; Lei Zhu; Yujie Wen; Yixiao Zhang; Tian Qin; Jia Wang; Tao Liu; Xifeng Xia; Di Wu; Xue-Qing Gong; Weiping Tang; Weiping Ding; Xi Liu; Liwei Chen; Clare P Grey; Luming Peng

doi:10.1039/d2sc03885d

Surface differences of oxide nanocrystals determined by geometry and exogenously coordinated water molecules

Chem Sci. 2022 Sep 14;13(37):11083-11090. doi: 10.1039/d2sc03885d. eCollection 2022 Sep 28.

Authors

Junchao Chen^{1

2}, Xin-Ping Wu³, Michael A Hope⁴, Zhiye Lin¹, Lei Zhu⁵, Yujie Wen¹, Yixiao Zhang², Tian Qin², Jia Wang³, Tao Liu⁶, Xifeng Xia⁷, Di Wu⁸, Xue-Qing Gong³, Weiping Tang⁵, Weiping Ding¹, Xi Liu², Liwei Chen^{2

9}, Clare P Grey⁴, Luming Peng^{1

10

11}

Affiliations

¹ Key Laboratory of Mesoscopic Chemistry of MOE, Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University 163 Xianlin Road Nanjing 210023 China luming@nju.edu.cn.
² School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, In situ Center for Physical Sciences, Shanghai Jiao Tong University Shanghai 200240 China.
³ Key Laboratory for Advanced Materials, Centre for Computational Chemistry, Research Institute of Industrial Catalysis, East China University of Science and Technology 130 Meilong Road Shanghai 200237 China.
⁴ Department of Chemistry, University of Cambridge Lensfield Road Cambridge CB2 1EW UK.
⁵ State Key Laboratory of Space Power Technology, Shanghai Institute of Space Power-Sources (SISP), Shanghai Academy of Spaceflight Technology Shanghai 200245 China.
⁶ Shanghai Key Laboratory of Chemical Assessment and Sustainability, Department of Chemistry, Tongji University Shanghai 200092 China.
⁷ Analysis and Testing Center, Nanjing University of Science and Technology Nanjing 210094 China.
⁸ College of Food Science and Engineering/Collaborative Innovation Center for Modern Grain Circulation and Safety/Key Laboratory of Grains and Oils Quality Control and Processing, Nanjing University of Finance and Economics Nanjing 210023 China.
⁹ i-Lab, CAS Center for Excellence in Nanoscience, Suzhou Institute of Nano-Tech and Nano-Bionics (SINANO), Chinese Academy of Sciences Suzhou 215123 China.
¹⁰ Jiangsu Key Laboratory of Vehicle Emissions Control, Nanjing University Nanjing 210093 China.
¹¹ Frontiers Science Center for Critical Earth Material Cycling (FSC-CEMaC), Nanjing University Nanjing Jiangsu 210023 China.

Abstract

Determining the different surfaces of oxide nanocrystals is key in developing structure-property relations. In many cases, only surface geometry is considered while ignoring the influence of surroundings, such as ubiquitous water on the surface. Here we apply ¹⁷O solid-state NMR spectroscopy to explore the facet differences of morphology-controlled ceria nanocrystals considering both geometry and water adsorption. Tri-coordinated oxygen ions at the 1^st layer of ceria (111), (110), and (100) facets exhibit distinct ¹⁷O NMR shifts at dry surfaces while these ¹⁷O NMR parameters vary in the presence of water, indicating its non-negligible effects on the oxide surface. Thus, the interaction between water and oxide surfaces and its impact on the chemical environment should be considered in future studies, and solid-state NMR spectroscopy is a sensitive approach for obtaining such information. The work provides new insights into elucidating the surface chemistry of oxide nanomaterials.