Surface structure of hydroxylated and sulfated zirconia. A periodic density-functional study

被引:80
作者
Hofmann, A [1 ]
Sauer, J [1 ]
机构
[1] Humboldt Univ, Inst Chem, D-10099 Berlin, Germany
关键词
D O I
10.1021/jp049220f
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
The surface structure of sulfated zirconia (SZ) is examined by density-functional theory (DFT) with periodic boundary conditions. Adsorption of H2O and SO3 (or H2SO4) on the (101) surface of tetragonal zirconia is studied for different loadings up to H2SO4.3H(2)O and 2H(2)SO(4).2H(2)O per two surface unit cells (four Zr surface sites). The considered surface species include H2O, [H+,OH-], SO3, [H+, HSO4-], [2H(+),SO42-], [H+,HS2O7-], and [2H(+),S2O72-]. Statistical thermodynamics is used to evaluate the relative stability of different surface structures for different temperatures and pressures of H2O and SO3 (or H2SO4). The simulated surface phase diagrams show a strong dependency on the considered sulfur species (H2SO4 or SO3) as well as on pressure and temperature. Monosulfates and pyrosulfates may occur, but higher condensated sulfates are not observed. In agreement with infrared experiments, we predict transformation of water-rich structures, [SO42-, 2H(+),3H(2)O(+)], into pyrosulfate structures, [S2O72-, 2H(+),H2O], during calcination. Further increase of the temperature yields adsorbed SO3 before the clean surface is reached. Water adsorbed on the t-ZrO2(101) surface leaves in three steps upon heating from 250 to 730 K at 0.01 bar pressure: physisorbed water below room temperature, the first chemisorbed water at about 440 K and the last water at about 730 K.
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页码:14652 / 14662
页数:11
相关论文
共 42 条
[1]   THE SUPERACIDITY OF SULFATED ZIRCONIA - AN AB-INITIO QUANTUM-MECHANICAL STUDY [J].
BABOU, F ;
BIGOT, B ;
SAUTET, P .
JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (44) :11501-11509
[2]  
BABOU F, 1994, STRUCTURE DYNAMICS E, V90
[3]   Interaction of sulfate groups with the surface of zirconia: An HRTEM characterization study [J].
Benaissa, M ;
Santiesteban, JG ;
Diaz, G ;
Chang, CD ;
JoseYacaman, M .
JOURNAL OF CATALYSIS, 1996, 161 (02) :694-703
[4]   Effect of sulfation on the acid-base properties of tetragonal zirconia. A calorimetric and IR spectroscopic study [J].
Bolis, V ;
Magnacca, G ;
Cerrato, G ;
Morterra, C .
TOPICS IN CATALYSIS, 2002, 19 (3-4) :259-269
[5]  
Frisch M.J., 2016, Gaussian 16 Revision C. 01. 2016, V01
[6]   The surface structure of sulfated zirconia:: Periodic ab initio study of sulfuric acid adsorbed on ZrO2(101) and ZrO2(001) [J].
Haase, F ;
Sauer, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (51) :13503-13512
[7]   NMR and theoretical study of acidity probes on sulfated zirconia catalysts [J].
Haw, JF ;
Zhang, JH ;
Shimizu, K ;
Venkatraman, TN ;
Luigi, DP ;
Song, WG ;
Barich, DH ;
Nicholas, JB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (50) :12561-12570
[8]   SOLID CATALYST TREATED WITH ANION .1. CATALYTIC ACTIVITY OF IRON-OXIDE TREATED WITH SULFATE ION FOR DEHYDRATION OF 2-PROPANOL AND ETHANOL AND POLYMERIZATION OF ISOBUTYL VINYL ETHER [J].
HINO, M ;
ARATA, K .
CHEMISTRY LETTERS, 1979, (05) :477-480
[9]   SOLID CATALYST TREATED WITH ANION .2. REACTIONS OF BUTANE AND ISOBUTANE CATALYZED BY ZIRCONIUM-OXIDE TREATED WITH SULFATE ION - SOLID SUPERACID CATALYST [J].
HINO, M ;
KOBAYASHI, S ;
ARATA, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (21) :6439-6441
[10]   SOLID CATALYSTS TREATED WITH ANIONS - SYNTHESIS OF SOLID SUPERACID CATALYST WITH ACID STRENGTH OF H0 LESS-THAN-OR-EQUAL-TO-16.04 [J].
HINO, M ;
ARATA, K .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1980, (18) :851-852