Higher alcohols synthesis from syngas over CoCu/SiO2 catalysts: Dynamic structure and the role of Cu

被引:104
作者
Su, Junjie [1 ]
Zhang, Zhengpai [1 ]
Fu, Donglong [1 ]
Liu, Da [1 ]
Xu, Xin-Chao [1 ]
Shi, Bianfang [1 ]
Wang, Xu [2 ]
Si, Rui [2 ]
Jiang, Zheng [2 ]
Xu, Jing [1 ]
Han, Yi-Fan [1 ,3 ]
机构
[1] E China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China
[2] Chinese Acad Sci, Shanghai Inst Appl Phys, Shanghai Synchrotron Radiat Facil, Shanghai 201204, Peoples R China
[3] Zhengzhou Univ, Sch Chem Engn & Energy, Res Ctr Heterogeneous Catalysis & Engn Sci, Zhengzhou 450001, Peoples R China
基金
中国国家自然科学基金;
关键词
Higher alcohols synthesis; Intrinsic kinetics; Syngas; Bimetallic CoCu catalysts; Promotional effects; FISCHER-TROPSCH SYNTHESIS; METHANOL SYNTHESIS; CO HYDROGENATION; SYNTHESIS GAS; FT-IR; COBALT; MECHANISM; EXAFS; HYDROCARBONS; NANOPARTICLES;
D O I
10.1016/j.jcat.2016.01.015
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
A comparative study of higher alcohols synthesis directly from syngas has been performed over monometallic Co and bimetallic CoCu/SiO2 catalysts. Particularly, the role of Cu on the origin. of active sites and reaction mechanism were investigated thoroughly using multiple techniques such as ex situ X-rays diffraction (XRD), X-ray absorption spectroscopy (XAS) and Raman spectroscopy. Reduction process of CoCu/SiO2 catalysts was also determined using in situ XRD and in situ Raman spectroscopy while the surface structure of reduced catalysts was detected by CO-DRIFTS. CoCu bimetallic particles covered by Cu atoms are responsible for alcohols synthesis. The intrinsic kinetics was performed over both catalysts under realistic reaction conditions. By comparing the kinetic parameters, including apparent activation energies and reaction orders, the promotional effects of Cu have been identified as: (1) weakening the CO/HCO dissociation and reducing the formation of CH species; (2) controlling surface Co ensemble size and inhibiting CHx insertion. (C) 2016 Elsevier Inc. All rights reserved.
引用
收藏
页码:94 / 106
页数:13
相关论文
共 53 条
[1]  
[Anonymous], 2014, ANGEW CHEM-GER EDIT, DOI DOI 10.1002/ANGE.201402680
[2]  
[Anonymous], ADV CATAL
[3]   EXAFS determination of the size of Co clusters on silica [J].
Arcon, I ;
Tuel, A ;
Kodre, A ;
Martin, G ;
Barbier, A .
JOURNAL OF SYNCHROTRON RADIATION, 2001, 8 :575-577
[4]   Structural investigations of copper doped B2O3-Bi2O3 glasses with high bismuth oxide content [J].
Baia, L ;
Stefan, R ;
Kiefer, W ;
Popp, J ;
Simon, S .
JOURNAL OF NON-CRYSTALLINE SOLIDS, 2002, 303 (03) :379-386
[5]  
Behrens M, 2012, SCIENCE, V336, P893, DOI [10.1126/science.1219831, 10.1126/science.12198331]
[6]   Dealloying of Cobalt from CuCo Nanoparticles under Syngas Exposure [J].
Carenco, Sophie ;
Tuxen, Anders ;
Chintapalli, Mahati ;
Pach, Elzbieta ;
Escudero, Carlos ;
Ewers, Trevor D. ;
Jiang, Peng ;
Borondics, Ferenc ;
Thornton, Geoff ;
Alivisatos, A. Paul ;
Bluhm, Hendrik ;
Guo, Jinghua ;
Salmeron, Miguel .
JOURNAL OF PHYSICAL CHEMISTRY C, 2013, 117 (12) :6259-6266
[7]   Design of supported cobalt catalysts with maximum activity for the Fischer-Tropsch synthesis [J].
den Breejen, Johan P. ;
Sietsma, Jelle R. A. ;
Friedrich, Heiner ;
Bitter, Johannes H. ;
de Jong, Krijn P. .
JOURNAL OF CATALYSIS, 2010, 270 (01) :146-152
[8]   A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas [J].
Fang, Kegong ;
Li, Debao ;
Lin, Minggui ;
Xiang, Minglin ;
Wei, Wei ;
Sun, Yuhan .
CATALYSIS TODAY, 2009, 147 (02) :133-138
[9]  
Fischer F, 1926, Brennstoff-Chemie, V7, P97
[10]   Structure sensitivity of the Fischer-Tropsch activity and selectivity on alumina supported cobalt catalysts [J].
Fischer, N. ;
van Steen, E. ;
Claeys, M. .
JOURNAL OF CATALYSIS, 2013, 299 :67-80