TY - JOUR
T1 - Theoretical study of selective hydrogenolysis of methyl vinyl carbinol over Au-Ni bimetallic catalyst
T2 - Toward constructing a working hypothesis for the role of dichloroethane solvent and perimeter sites
AU - Ato, Yoshinori
AU - Hayashi, Akihide
AU - Sonoura, Ayaka
AU - Koga, Hiroaki
AU - Ishida, Tamao
AU - Tokunaga, Makoto
AU - Okumura, Mitsutaka
N1 - Funding Information:
This study was supported by a Grant-in-Aid for Scientific Research (c) (No. 17K05752 ), Japan and Elements Strategy Initiative for Catalysts and Batteries (ESICB) of the Ministry of Education, Culture, Sports, Science and Technology , Japan (MEXT). Molecular graphics and analyses were performed with VMD, Visual Molecular Dynamics, developed by the Theoretical Biophysics group at the University of Illinois and the Beckman Institute, with support from grants from the National Institutes of Health (grant number PHS 5 P41 RR05969-04), the National Science Foundation (grant number BIR-9423827 EQ), and the Roy J. Carver Charitable Trust [37] .
Publisher Copyright:
© 2020 Elsevier B.V.
PY - 2020/9
Y1 - 2020/9
N2 - Au-Ni bimetallic nanoparticles catalyze the hydrogenolysis of the hydroxy group of benzylic alcohols by activating H2 with dichloroethane solvent. To propose a working hypothesis for their reaction mechanism, we performed theoretical calculations for the hydroxylation of methyl vinyl carbinol over the Au1Ni19 cluster. The results showed that there're two reaction cycles, depending on the presence of HCl. Firstly, the solvent acted as a sacrificial reagent to produce the carbocation intermediate, while HCl was produced in other reaction. It was found that the presence of the exposed Au site played an important role for producing HCl and subsequent hydrogenolysis.
AB - Au-Ni bimetallic nanoparticles catalyze the hydrogenolysis of the hydroxy group of benzylic alcohols by activating H2 with dichloroethane solvent. To propose a working hypothesis for their reaction mechanism, we performed theoretical calculations for the hydroxylation of methyl vinyl carbinol over the Au1Ni19 cluster. The results showed that there're two reaction cycles, depending on the presence of HCl. Firstly, the solvent acted as a sacrificial reagent to produce the carbocation intermediate, while HCl was produced in other reaction. It was found that the presence of the exposed Au site played an important role for producing HCl and subsequent hydrogenolysis.
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U2 - 10.1016/j.cplett.2020.137773
DO - 10.1016/j.cplett.2020.137773
M3 - Article
AN - SCOPUS:85087993818
SN - 0009-2614
VL - 754
JO - Chemical Physics Letters
JF - Chemical Physics Letters
M1 - 137773
ER -