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E u r o s c i c o n C o n f e r e n c e o n
Physical Chemistry and
Analytical Separation Techniques
October 08-09 , 2018
Amsterdam, Nether l ands
Journal of Organic & Inorganic Chemistry
ISSN: 2472-1123
Physical Chemistry and Analytical Separation Techniques 2018
W
e have studied the mechanism of hydrogen production from methanol by two different and well known ruthenium based
molecular catalysts: Ru(trop)2dad complex and pincer supported Ru-PNP complex using density functional theory (DFT)
in conjunction with
ab initio
molecular dynamics studies (AIMD) with explicit solvation. The results show that while methanol
dehydrogenation occurs via a Noyori type (Ru-N) bi-functional mechanism by the Ru(trop)2dad catalyst, the RuPNP complex does
not feature the commonly assumed (Ru-N) bifunctional mechanism under the applied reaction conditions. Ru(trop)2dad catalyst
does not require any additive (base/Lewis acid) for activity while the RuPNP complex requires 8M KOH for optimal activity.
Several other well-known molecular catalysts also require an additive (base/Lewis acid) for hydrogen production from methanol.
Therefore, the mechanistic studies on Ru(trop)2dad and RuPNP systems, and the sharp contrast in their respective mechanistic
pathways provide guidelines for rational design of additive free and highly active bi-functional catalysts for hydrogen production
from methanol. Moreover, these case studies show the importance of an explicit consideration of solvent molecules for realistic
computational modelling of minimum energy reaction pathway.
v.sinha@uva.nlVivek Sinha
1
, N Govindarajan
2
, M Trincado
3
, E J Meijer
2
,
H Grutzmacher
3
and B de Bruin
1
1
HomKat, HIMS-University of Amsterdam, Netherlands
2
MolSim, HIMS-Universiteit van Amsterdam, The Netherlands
3
LAC-ETH Zuric, Switzerland
J Org Inorg Chem 2018 Volume: 4
DOI: 10.21767/2472-1123-C6-018
How to design a bi-functional molecular catalyst
for hydrogen production from methanol?