TY - JOUR
T1 - Formation of propane in the aqueous-phase processing of 1-propanol over platinum
T2 - A DFT study
AU - Chiu, Cheng chau
AU - Genest, Alexander
AU - Rösch, Notker
PY - 2013/11
Y1 - 2013/11
N2 - The reaction pathways for alkane formation from alcohols in aqueous-phase (AP) processing was studied computationally for the model system 1-propanol over flat and stepped surfaces of Pt. We examined the dehydration-hydrogenation (DH) mechanism in an acidic environment and alcohol hydrogenolysis (AH) under neutral conditions. The highest (relative) barrier of the DH mechanism was calculated at approximately 90kJmol-1 on Pt(111), which occurs in the hydrogenation step after cleavage of the C - O bond. The highest relative barrier of the AH mechanism, if the C - O bond is cleaved on Pt(111), is slightly higher, 105kJmol-1. The corresponding elementary reaction step does not start from the alcohol, but a dehydrogenated intermediate. On Pt(221), transition state geometries differ somewhat and the highest relative barriers of both mechanisms, AH and DH, are lower by 8-40kJmol-1, than the corresponding barriers on Pt(111).
AB - The reaction pathways for alkane formation from alcohols in aqueous-phase (AP) processing was studied computationally for the model system 1-propanol over flat and stepped surfaces of Pt. We examined the dehydration-hydrogenation (DH) mechanism in an acidic environment and alcohol hydrogenolysis (AH) under neutral conditions. The highest (relative) barrier of the DH mechanism was calculated at approximately 90kJmol-1 on Pt(111), which occurs in the hydrogenation step after cleavage of the C - O bond. The highest relative barrier of the AH mechanism, if the C - O bond is cleaved on Pt(111), is slightly higher, 105kJmol-1. The corresponding elementary reaction step does not start from the alcohol, but a dehydrogenated intermediate. On Pt(221), transition state geometries differ somewhat and the highest relative barriers of both mechanisms, AH and DH, are lower by 8-40kJmol-1, than the corresponding barriers on Pt(111).
KW - Alcohols
KW - Density functional calculations
KW - Heterogeneous catalysis
KW - Hydrogenation
KW - Platinum
UR - http://www.scopus.com/inward/record.url?scp=84889593201&partnerID=8YFLogxK
U2 - 10.1002/cctc.201300184
DO - 10.1002/cctc.201300184
M3 - Article
AN - SCOPUS:84889593201
SN - 1867-3880
VL - 5
SP - 3299
EP - 3308
JO - ChemCatChem
JF - ChemCatChem
IS - 11
ER -