Isolated FeII on Silica As a Selective Propane Dehydrogenation Catalyst

被引:171
作者
Hu, Bo [1 ]
Schweitzer, Neil M. [2 ]
Zhang, Guanghui [2 ,3 ]
Kraft, Steven J. [2 ]
Childers, David J. [4 ]
Lanci, Michael P. [2 ]
Miller, Jeffrey T. [2 ]
Hock, Adam S. [1 ,2 ]
机构
[1] IIT, Dept Chem, Chicago, IL 60616 USA
[2] Argonne Natl Lab, Chem Sci & Engn Div, Argonne, IL 60439 USA
[3] Wuhan Univ, Coll Chem & Mol Sci, Wuhan 430072, Peoples R China
[4] Univ Illinois, Dept Chem Engn, Chicago, IL 60607 USA
关键词
isolated Fe catalysts; propane dehydrogenation; Fe nanoparticles on silica; dehydrogenation catalyst; Fe XANES; EXAFS; CHROMIUM-OXIDE CATALYSTS; H BOND ACTIVATION; X-RAY-ABSORPTION; SINGLE-SITE; HETEROGENEOUS CATALYSIS; SUPPORTED CATALYSTS; CARBON-DIOXIDE; GALLIUM OXIDE; IRON-OXIDES; COMPLEXES;
D O I
10.1021/acscatal.5b00248
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
We report a comparative study of isolated Fe-II, iron oxide particles, and metallic nanoparticles on silica for non-oxidative propane dehydrogenation. It was found that the most selective catalyst was an isolated Fe-II species on silica prepared by grafting the open cyclopentadienide iron complex, bis(2,4-dimethyl-1,3-pentadienide) iron(II) or Fe(oCp)(2). The grafting and evolution of the surface species was elucidated by H-1 NMR, diffuse reflectance infrared Fourier transform spectroscopy and X-ray absorption spectroscopies. The oxidation state and local structure of surface Fe were characterized by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure. The initial grafting of iron proceeds by one surface hydroxyl SiOH reacting with Fe(oCp)(2) to release one diene ligand (oCpH), generating a SiO2-bound Fe-II(oCp) species, 1-FeoCp. Subsequent treatment with H-2 at 400 degrees C leads to loss of the remaining diene ligand and formation of nanosized iron oxide clusters, 1-C. Dispersion of these Fe oxide clusters occurs at 650 degrees C, forming an isolated, ligand-free Fe-II on silica, 1-Fe-II, which is catalytically active and highly selective (similar to 99%) for propane dehydrogenation to propene. Under reaction conditions, there is no evidence of metallic Fe by in situ XANES. For comparison, metallic Fe nanoparticles, 2-NP-Fe-0, were independently prepared by grafting Fe[N(SiMe3)(2)](2) onto silica, 2-FeN*, and reducing it at 650 degrees C in H-2. The Fe NPs were highly active for propane conversion but showed poor selectivity (similar to 14%) to propene. Independently prepared Fe oxide clusters on silica display a low activity. The sum of these results suggests that selective propane dehydrogenation occurs at isolated Fe-II sites.
引用
收藏
页码:3494 / 3503
页数:10
相关论文
共 70 条
[1]   Physicochemical properties and catalytic performance of galloaluminosilicate in aromatization of lower alkanes: a comparative study with Ga/HZSM-5 [J].
Al-Yassir, N. ;
Akhtar, M. N. ;
Al-Khattaf, S. .
JOURNAL OF POROUS MATERIALS, 2012, 19 (06) :943-960
[2]   SYNTHESIS OF BIS[BIS(TRIMETHYLSILYL)AMIDO]IRON(II) - STRUCTURE AND BONDING IN MN[N(SIME3)2]2, FE[N(SIME3)2]2, CO[N(SIME3)2]2 - 2-COORDINATE TRANSITION-METAL AMIDES [J].
ANDERSEN, RA ;
FAEGRI, K ;
GREEN, JC ;
HAALAND, A ;
LAPPERT, MF ;
LEUNG, WP ;
RYPDAL, K .
INORGANIC CHEMISTRY, 1988, 27 (10) :1782-1786
[3]  
Bart S. C., 2006, J AM CHEM SOC, V128, P5302
[4]   Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation [J].
Bart, SC ;
Lobkovsky, E ;
Chirik, PJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (42) :13794-13807
[5]   Electronic structure of bis(imino)pyridine iron dichloride, monochloride, and neutral ligand complexes: A combined structural, spectroscopic, and computational study [J].
Bart, Suzanne C. ;
Chlopek, Krzysztof ;
Bill, Eckhard ;
Bouwkamp, Marco W. ;
Lobkovsky, Emil ;
Neese, Frank ;
Wieghardt, Karl ;
Chirik, Paul J. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (42) :13901-13912
[6]   Structure and function of metal cations in light alkane reactions catalyzed by modified H-ZSM5 [J].
Biscardi, JA ;
Iglesia, E .
CATALYSIS TODAY, 1996, 31 (3-4) :207-231
[7]   Non-oxidative reactions of propane on Zn/Na-ZSM5 [J].
Biscardi, JA ;
Iglesia, E .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1999, 1 (24) :5753-5759
[8]   Highly active, stable, and selective well-defined silica supported Mo imido olefin metathesis catalysts [J].
Blanc, Frederic ;
Thivolle-Cazat, Jean ;
Basset, Jean-Marie ;
Coperet, Christophe ;
Hock, Adam S. ;
Tonzetich, Zachary J. ;
Schrock, Richard. R. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (05) :1044-1045
[9]   Thermal spreading of MoO3 onto silica supports [J].
Braun, S ;
Appel, LG ;
Camorim, VL ;
Schmal, M .
JOURNAL OF PHYSICAL CHEMISTRY B, 2000, 104 (28) :6584-6590
[10]   Influence of surface modification of Ti-SBA15 catalysts on the epoxidation mechanism for cyclohexene with aqueous hydrogen peroxide [J].
Brutchey, RL ;
Ruddy, DA ;
Andersen, LK ;
Tilley, TD .
LANGMUIR, 2005, 21 (21) :9576-9583