Graphitic mesoporous carbon-supported molybdenum carbides for catalytic hydrogenation of carbon monoxide to mixed alcohols

被引:26
作者
Chai, Song-Hai [1 ]
Schwartz, Viviane [2 ]
Howe, Jane Y. [3 ]
Wang, Xiqing [1 ]
Kidder, Michelle [1 ]
Overbury, Steven H. [1 ,2 ]
Dai, Sheng [1 ,2 ,4 ]
Jiang, De-en [1 ]
机构
[1] Oak Ridge Natl Lab, Div Chem Sci, Oak Ridge, TN 37831 USA
[2] Oak Ridge Natl Lab, Ctr Nanophase Mat Sci, Oak Ridge, TN 37831 USA
[3] Oak Ridge Natl Lab, Mat Sci & Technol Div, Oak Ridge, TN 37831 USA
[4] Univ Tennessee, Dept Chem, Knoxville, TN 37966 USA
关键词
Mesoporous carbon; Molybdenum carbides; Heterogeneous catalysis; Synthesis gas conversion; Alcohol synthesis; SYNTHESIS GAS CONVERSION; CO HYDROGENATION; SURFACE-AREA; TUNGSTEN CARBIDES; BLOCK-COPOLYMERS; SYNGAS; ADSORPTION; REDUCTION; SULFIDE; ETHANOL;
D O I
10.1016/j.micromeso.2012.11.025
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
Molybdenum carbide (beta-Mo2C) nanoparticles were synthesized in situ on a soft-templated graphitic mesoporous carbon (GMC) and other commercial carbon materials (activated charcoal and carbon black) by carbothermal hydrogen reduction (i.e., carbon supports as carburizing agents). The catalytic activity of these carbon-supported and bulk carbides for carbon monoxide (CO) hydrogenation to mixed alcohols (mainly C-1-C-3) was investigated at 573 K and 3.0 MPa, showing that their areal specific rates for CO conversion increase with decreasing the carbide particle size, independent of the supports. GMC appears to be a preferable support of beta-Mo2C to activated charcoal and carbon black because of its ability for the formation of smaller carbide particles resulting in higher catalytic activity. Addition of a minor amount of K2CO3 into beta-Mo2C/GMC (molar K/Mo = 0.05-0.5) promotes the formation of higher alcohols (C2+-OH) considerably, leading to a maximum space time yield (STY) for C2+-OH at medium K/Mo ratio of 0.1. Compared with typical Rh/GMC catalyst promoted triply with Mn, Li, and Fe oxides, the K2CO3-promoted beta-Mo2C/GMC catalyst shows higher C2+-OH selectivity (30 vs. 25 mol-C% on CO2-free basis) and STY (71 vs. 46 mg (h g(cat))(-1)) in spite of its suppressed formation of CH3OH. (C) 2012 Elsevier Inc. All rights reserved.
引用
收藏
页码:141 / 149
页数:9
相关论文
共 52 条
[21]   Synthesis of mesoporous carbon materials via enhanced hydrogen-bonding interaction [J].
Liang, CD ;
Dai, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (16) :5316-5317
[22]   Synthesis of a large-scale highly ordered porous carbon film by self-assembly of block copolymers [J].
Liang, CD ;
Hong, KL ;
Guiochon, GA ;
Mays, JW ;
Dai, S .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (43) :5785-5789
[23]   Activated carbon supported bimetallic CoMo carbides synthesized by carbothermal hydrogen reduction [J].
Liang, CH ;
Ma, WP ;
Feng, ZC ;
Li, C .
CARBON, 2003, 41 (09) :1833-1839
[24]   Nanostructured β-Mo2C prepared by carbothermal hydrogen reduction on ultrahigh surface area carbon material [J].
Liang, CH ;
Ying, PL ;
Li, C .
CHEMISTRY OF MATERIALS, 2002, 14 (07) :3148-3151
[25]   Co-decorated carbon nanotube-supported Co-Mo-K sulfide catalyst for higher alcohol synthesis [J].
Ma, Xiao-Ming ;
Lin, Guo-Dong ;
Zhang, Hong-Bin .
CATALYSIS LETTERS, 2006, 111 (3-4) :141-151
[26]   Elementary steps of syngas reactions on Mo2C(001): Adsorption thermochemistry and bond dissociation [J].
Medford, Andrew J. ;
Vojvodic, Aleksandra ;
Studt, Felix ;
Abild-Pedersen, Frank ;
Norskov, Jens K. .
JOURNAL OF CATALYSIS, 2012, 290 :108-117
[27]  
Natta G., 1957, CATALYSIS, V5, P131
[28]   Carbon monoxide hydrogenation over molybdenum and tungsten carbides [J].
Patterson, PM ;
Das, TK ;
Davis, BH .
APPLIED CATALYSIS A-GENERAL, 2003, 251 (02) :449-455
[29]   Low temperature water-gas shift:: The effect of alkali doping on the C-H bond of formate over Pt/ZrO2 catalysts [J].
Pigos, John M. ;
Brooks, Christopher J. ;
Jacobs, Gary ;
Davis, Burtron H. .
APPLIED CATALYSIS A-GENERAL, 2007, 328 (01) :14-26
[30]   CATALYSIS OVER MOLYBDENUM CARBIDES AND NITRIDES .1. CATALYST CHARACTERIZATION [J].
RANHOTRA, GS ;
HADDIX, GW ;
BELL, AT ;
REIMER, JA .
JOURNAL OF CATALYSIS, 1987, 108 (01) :24-39