CO temperature-programmed desorption of a hexameric copper hydride nanocluster catalyst supported on functionalized MWCNTs for active site characterization in a low-temperature water-gas shift reaction

被引:13
作者
Baharudin, Luqmanulhakim [1 ]
Yip, Alex C. K. [1 ]
Golovko, Vladimir B. [2 ]
Polson, Matthew I. J. [2 ]
Watson, Matthew J. [1 ]
机构
[1] Univ Canterbury, Dept Chem & Proc Engn, Coll Engn, Private Bag 4800, Christchurch 8140, New Zealand
[2] Univ Canterbury, Sch Phys & Chem Sci, Coll Sci, Private Bag 4800, Christchurch 8140, New Zealand
关键词
Active site characterization; Copper nanoclusters; CO chemisorption; CO temperature-programmed desorption; Multi-walled carbon nanotubes; Water-gas shift; METHANOL SYNTHESIS; STRUCTURAL-CHARACTERIZATION; MICROKINETIC MODEL; OXIDATION; HYDROGEN; LAYER; CU2O; IRON;
D O I
10.1016/j.cej.2018.10.215
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
A family of novel catalysts was generated using chemically synthesised, atomically precise hexameric copper hydride nanoclusters (Cu-6) deposited on carboxyl-pre-functionalized multi-walled carbon nanotubes (MWCNTCOOH). The Cu-6/MWCNTCOOH catalysts were synthesized by wet impregnation of MWCNTCOOH with varying copper loading contents (0.5-15 wt%). The study of the interaction between active sites in these materials with CO at low temperatures using CO temperature-programmed desorption in conjunction with the elementary steps in the Langmuir-Hinshelwood mechanism of low-temperature water-gas shift (LTWGS) reaction allowed us to predict the potential catalytic performance of the synthesized catalysts in the LTWGS. The hypothetical activities were correlated with the catalyst surface characterization by CO chemisorption (Cu dispersion, crystallite size and surface area) and characterization of the active phase composition by XRD, showing good agreement. Optimal copper loading was identified to be 1 wt% based on the highest Cu surface area per sample weight and dispersion, and the amount of CO adsorbed per sample weight. The predicted catalytic performance was analysed as a function of support type: MWCNTCOOH cf. non-functionalized MWCNTs and alumina with fixed Cu loading of 1 wt%. The CO reactivity was analysed on Cu2O crystallites as the active phase, with a focus on the most dominant facets: (1 1 0), (1 1 1), (2 0 0) and (2 2 0). A comparison was made with a sample consisting of Cu nanoparticles (Cu-NP) supported on MWCNTCOOH, and a reference commercial catalyst, 51% CuO/31% ZnO-Al2O3. It is expected that the optimal catalyst, 1% Cu-6/MWCNTCOOH, is active for LTWGS reaction from temperatures as low as 120 degrees C (governed by dew point of water) up to temperatures well below industrial operating temperatures (constrained by temperature rise due to the exothermic reaction that leads to Cu-6 sintering).
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页数:12
相关论文
共 36 条
[1]   LEWIS-BASE ADDUCTS OF GROUP-11 METAL(I) COMPOUNDS .49. STRUCTURAL CHARACTERIZATION OF HEXAMERIC AND PENTAMERIC (TRIPHENYLPHOSPHINE)COPPER(I) HYDRIDES [J].
ALBERT, CF ;
HEALY, PC ;
KILDEA, JD ;
RASTON, CL ;
SKELTON, BW ;
WHITE, AH .
INORGANIC CHEMISTRY, 1989, 28 (07) :1300-1306
[2]   Reverse water-gas shift reaction at the Cu/ZnO interface: Influence of the Cu/Zn ratio on structure-activity correlations [J].
Alvarez Galvan, Consuelo ;
Schumann, Julia ;
Behrens, Malte ;
Garcia Fierro, Jose Luis ;
Schloegl, Robert ;
Frei, Elias .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2016, 195 :104-111
[3]   Potential of metal monoliths with grown carbon nanomaterials as catalyst support in intensified steam reformer: a perspective [J].
Baharudin, Luqmanulhakim ;
Yip, Alex Chi-Kin ;
Golovko, Vladimir ;
Watson, Matthew .
REVIEWS IN CHEMICAL ENGINEERING, 2020, 36 (04) :459-491
[4]   Hydrogen applications and research activities in its production routes through catalytic hydrocarbon conversion [J].
Baharudin, Luqmanulhakim ;
Watson, Matthew James .
REVIEWS IN CHEMICAL ENGINEERING, 2018, 34 (01) :43-72
[5]   An improved microkinetic model for the water gas shift reaction on copper [J].
Callaghan, C ;
Fishtik, I ;
Datta, R ;
Carpenter, M ;
Chmielewski, M ;
Lugo, A .
SURFACE SCIENCE, 2003, 541 (1-3) :21-30
[6]   PROMOTION OF METHANOL SYNTHESIS AND THE WATER-GAS SHIFT REACTIONS BY ADSORBED OXYGEN ON SUPPORTED COPPER-CATALYSTS [J].
CHINCHEN, GC ;
SPENCER, MS ;
WAUGH, KC ;
WHAN, DA .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS I, 1987, 83 :2193-2212
[7]   How Carbon-Nano-Fibers attach to Ni foam [J].
Chinthaginjala, J. K. ;
Thakur, D. B. ;
Seshan, K. ;
Lefferts, L. .
CARBON, 2008, 46 (13) :1638-1647
[8]   Influence of hydrogen on the formation of a thin layer of carbon nanofibers on Ni foam [J].
Chinthaginjala, J. K. ;
Lefferts, L. .
CARBON, 2009, 47 (14) :3175-3183
[9]  
Cook A. W., 2016, INORG CHEM
[10]   Carbon-supported copper catalysts I. Characterization [J].
Dandekar, A ;
Baker, RTK ;
Vannice, MA .
JOURNAL OF CATALYSIS, 1999, 183 (01) :131-154