TY - JOUR
T1 - Aerobic oxidation of alkanes on icosahedron gold nanoparticle Au55
AU - Staykov, Aleksandar
AU - Miwa, Tetsuya
AU - Yoshizawa, Kazunari
N1 - Funding Information:
This work was supported by KAKENHI Grant numbers JP24109014 , JP15K13710 , and JP17H03117 from Japan Society for the Promotion of Science (JSPS) and the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT) , the MEXT Projects of “World Premier International Research Center Initiative (WPI),” “Integrated Research Consortium on Chemical Sciences,” and “Elements Strategy Initiative to Form Core Research Center,” and JST-CREST JPMJCR15P5 .
PY - 2018/8
Y1 - 2018/8
N2 - Aerobic oxidation of cyclohexane, propane, ethane, and methane to the corresponding alcohols was investigated over an Au55 gold nanoparticle with icosahedron symmetry using density functional theory. Reaction mechanisms were elucidated and activation barriers for catalytic C–H bond cleavage and corresponding alcohols’ formation were estimated. Furthermore, on the basis of the reaction rate constants calculated for realistic reaction temperatures, the relative reaction rates for each alkane hydroxylation were discussed. The catalyst selectivity was investigated for the formation of primary and secondary alcohols. All reaction mechanisms for alkane hydroxylation are compared with the catalytic dissociation of dioxygen molecule over gold nanoparticle surface, which is an important precursor reaction for aerobic oxidation. We have further investigated overoxidation reaction mechanisms leading to formation of ketones. Our results are compared with experimental findings to provide important guidelines for the tuning of catalytic reactions towards the desired products and reaction conditions.
AB - Aerobic oxidation of cyclohexane, propane, ethane, and methane to the corresponding alcohols was investigated over an Au55 gold nanoparticle with icosahedron symmetry using density functional theory. Reaction mechanisms were elucidated and activation barriers for catalytic C–H bond cleavage and corresponding alcohols’ formation were estimated. Furthermore, on the basis of the reaction rate constants calculated for realistic reaction temperatures, the relative reaction rates for each alkane hydroxylation were discussed. The catalyst selectivity was investigated for the formation of primary and secondary alcohols. All reaction mechanisms for alkane hydroxylation are compared with the catalytic dissociation of dioxygen molecule over gold nanoparticle surface, which is an important precursor reaction for aerobic oxidation. We have further investigated overoxidation reaction mechanisms leading to formation of ketones. Our results are compared with experimental findings to provide important guidelines for the tuning of catalytic reactions towards the desired products and reaction conditions.
UR - http://www.scopus.com/inward/record.url?scp=85047905690&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85047905690&partnerID=8YFLogxK
U2 - 10.1016/j.jcat.2018.05.017
DO - 10.1016/j.jcat.2018.05.017
M3 - Article
AN - SCOPUS:85047905690
VL - 364
SP - 141
EP - 153
JO - Journal of Catalysis
JF - Journal of Catalysis
SN - 0021-9517
ER -