TY - JOUR
T1 - Molecular catalysis for the steam reforming of ethanol
AU - Lin, Jianyi
AU - Chen, Luwei
AU - Choong, Catherine Kai Shin
AU - Zhong, Ziyi
AU - Huang, Lin
N1 - Publisher Copyright:
© 2014 Science China Press and Springer-Verlag Berlin Heidelberg.
PY - 2015/1
Y1 - 2015/1
N2 - In this paper, the application of molecular catalysis for steam reforming of ethanol (SRE) is reviewed. Eight metals (Ni, Co, Cu, Pt, Rh, Pd, Ir and Ru) have shown high catalytic activity for SRE. Among them Ni and Rh are very promising because of high d character in the metal bond and low metal-oxygen bonding (vs. metal-carbon). They can effectively promote C-C bond cleavage in the rate-determining process during SRE. However, Rh is weak in water-gas-shift so that CH4 and CO become the main by-products at low reaction temperatures, while Ni catalysts suffer from rapid deactivation due to coking and sintering. Two low-temperature CO-free catalysts have been developed in our lab, namely Rh-Fe/Ca-Al2O3 and carbonyl-derived Rh-Co/CeO2, in which the presence of iron oxide or Co can promote water-gas-shift reaction and significantly improve the SRE performance. On the other hand, adding 3 wt% CaO to Ni/Al2O3 can greatly improve the catalyst stability because the Ca modification not only increases Ni concentration on the Ni/Ca-Al2O3 surface and 3d valence electron density, but also facilitates the water adsorption and coke gasification via water-gas-shift. The availability of abundant surface OH groups helps the formation and conversion of adsorbed formate intermediate. Hence, ethanol reaction on Ca-Al2O3-supported Ni, Pt, Pd and Rh catalysts are found to follow the formate-intermediated pathway, a new reaction pathway alternative to the traditional acetate-intermediated pathway.
AB - In this paper, the application of molecular catalysis for steam reforming of ethanol (SRE) is reviewed. Eight metals (Ni, Co, Cu, Pt, Rh, Pd, Ir and Ru) have shown high catalytic activity for SRE. Among them Ni and Rh are very promising because of high d character in the metal bond and low metal-oxygen bonding (vs. metal-carbon). They can effectively promote C-C bond cleavage in the rate-determining process during SRE. However, Rh is weak in water-gas-shift so that CH4 and CO become the main by-products at low reaction temperatures, while Ni catalysts suffer from rapid deactivation due to coking and sintering. Two low-temperature CO-free catalysts have been developed in our lab, namely Rh-Fe/Ca-Al2O3 and carbonyl-derived Rh-Co/CeO2, in which the presence of iron oxide or Co can promote water-gas-shift reaction and significantly improve the SRE performance. On the other hand, adding 3 wt% CaO to Ni/Al2O3 can greatly improve the catalyst stability because the Ca modification not only increases Ni concentration on the Ni/Ca-Al2O3 surface and 3d valence electron density, but also facilitates the water adsorption and coke gasification via water-gas-shift. The availability of abundant surface OH groups helps the formation and conversion of adsorbed formate intermediate. Hence, ethanol reaction on Ca-Al2O3-supported Ni, Pt, Pd and Rh catalysts are found to follow the formate-intermediated pathway, a new reaction pathway alternative to the traditional acetate-intermediated pathway.
KW - Ca-AlO support
KW - Ni catalysts
KW - Rh catalysts
KW - formate-intermediated pathway
KW - hydrogen production
KW - molecular catalysis
KW - steam reforming of ethanol
KW - support effects
UR - http://www.scopus.com/inward/record.url?scp=84925538454&partnerID=8YFLogxK
U2 - 10.1007/s11426-014-5262-0
DO - 10.1007/s11426-014-5262-0
M3 - 文章
AN - SCOPUS:84925538454
SN - 1674-7291
VL - 58
SP - 60
EP - 78
JO - Science China Chemistry
JF - Science China Chemistry
IS - 1
ER -
