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

被引：10

作者：

Huang, Daofeng ^{[1
,2
]}

Chen, Siyue ^{[3
]}

Ma, Sicong ^{[4
]}

Chen, Xin ^{[1
,2
]}

Ren, Yuanhang ^{[1
,2
]}

Wang, Meiyin ^{[1
,2
]}

Ye, Lin ^{[1
,2
]}

Zhang, Li ^{[1
,2
]}

Chen, Xueying ^{[1
,2
]}

Liu, Zhi-Pan ^{[3
]}

Yue, Bin ^{[1
,2
]}

He, Heyong ^{[1
,2
]}

机构：

[1] Fudan Univ, Dept Chem, Shanghai 200438, Peoples R China

[2] Fudan Univ, Shanghai Key Lab Mol Catalysis & Innovat Mat, Shanghai 200438, Peoples R China

[3] Fudan Univ, Collaborat Innovat Ctr Chem Energy Mat, Shanghai Key Lab Mol Catalysis & Innovat Mat, Dept Chem,Key Lab Computat Phys Sci, Shanghai 200438, Peoples R China

[4] Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Synthet & Self Assembly Chem Organ Funct, Shanghai 200032, Peoples R China

来源：

CATALYSIS SCIENCE & TECHNOLOGY | 2022年 / 12卷 / 02期

基金：

中国国家自然科学基金;

关键词：

SOLID-STATE NMR; AB-INITIO; P-31; NMR; PHASE-TRANSFORMATION; SUPERACID CATALYST; PERIODIC DFT; ZRO2; SITES; OXIDE; TRIMETHYLPHOSPHINE;

D O I：

10.1039/d1cy01860d

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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 P-31 MAS NMR using TMP as the probe molecule. In comparison with zirconia, stronger Lewis acid (LA) and Bronsted 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.

引用

页码：596 / 605

页数：10