Determination of acid structures on the surface of sulfated monoclinic and tetragonal zirconia through experimental and theoretical approaches

Daofeng Huang; Siyue Chen; Sicong Ma; Xin Chen; Yuanhang Ren; Meiyin Wang; Lin Ye; Li Zhang; Xueying Chen; Zhi-Pan Liu; Bin Yue; Heyong He

doi:10.1039/D1CY01860D

Determination of acid structures on the surface of sulfated monoclinic and tetragonal zirconia through experimental and theoretical approaches†

Daofeng Huang,^a Siyue Chen,^b Sicong Ma,

^c Xin Chen,^a Yuanhang Ren,

^a Meiyin Wang,^a Lin Ye,^a Li Zhang,^a Xueying Chen,^a Zhi-Pan Liu,

^b Bin Yue*^a and Heyong He

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438, P. R. China
E-mail: yuebin@fudan.edu.cn, heyonghe@fudan.edu.cn

^b Collaborative Innovation Center of Chemistry for Energy Material, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Key Laboratory of Computational Physical Science, Department of Chemistry, Fudan University, Shanghai 200438, China

^c Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

Abstract

Sulfated zirconia (SZ) plays an important role in solid acid catalysts. To understand the origin of the super acidity over the surface of sulfated zirconia, pure monoclinic and tetragonal phase zirconia and their sulfated counterparts (M-SZ and T-SZ, respectively) were prepared, and the acid properties of these samples were characterized by ³¹P MAS NMR using TMP as the probe molecule. In comparison with zirconia, stronger Lewis acid (LA) and Brønsted acid (BA) sites were generated over the SZ samples after sulfation. The density ratios of the newly generated LA and strong BA sites were found to be ca. 2.0 : 1.0 on M-SZ and ca. 1.8 : 1.0 on T-SZ. Based on this quantitative relationship between the newly generated LA and strong BA sites, the possible acid structures on the SZ surface with different crystal phases are established. After structural optimization and theoretical calculation, the super acid sites originating from the bisulfate ions on the monoclinic (001) plane and the tetragonal (111) plane are determined.

Catalysis Science & Technology

Determination of acid structures on the surface of sulfated monoclinic and tetragonal zirconia through experimental and theoretical approaches†

Abstract

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Determination of acid structures on the surface of sulfated monoclinic and tetragonal zirconia through experimental and theoretical approaches

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