Title

Author

DOI

DFT Study on the Homogeneous Guo-Ming Zhao,, HuiPalladium-Catalyzed

ling Liu,*, Xu-ri Huang,
NAlkylation of Amines with
Xue Yang, and Yu-peng
Alcohols
Xie
10.1021/acscatal.5b01043

Effect of Chloride Anions on the

Synthesis and Enhanced
Catalytic Activity of Silver
Nanocoral Electrodes for CO2
Electroreduction

Yu-Chi Hsieh, Sanjaya D.

Senanayake, Yu Zhang,
Wenqian Xu, and
Dmitry E. Polyansky
10.1021/acscatal.5b01235

Understanding the selectivity of

methanol steam reforming on
the (1 1 1) surfaces of NiZn,
PdZn and PtZn: Insights from
M. Krajc a, , A.-P. Tsai 10.1016/j.jcat.2015.06.0
DFT
b , J. Hafner
20

Maarten K. Sabbe,
Gonzalo CanduelaDFT-based modeling of benzene Rodriguez, Mariehydrogenation on Pt at
Franoise Reyniers ,
industrially relevant coverage
Guy B. Marin

10.1016/j.jcat.2015.08.003

Computational chemistry for

NH3 synthesis, hydrotreating,
and NOx reduction: Three topics Ahmed O. Elnabawy,
of special interest to Haldor
Srinivas Rangarajan,
Topse
Manos Mavrikakis

10.1016/j.jcat.2014.12.0
18

Electrochemical Formation of
Reactive Oxygen Species at Pt
(111)--A Density Functional
Theory Study

Mohammad J.
Eslamibidgoli and
Michael H. Eikerling

10.1021/acscatal.5b01154

Mechanistic studies of aldol

condensations in UiO-66 and
UiO-66-NH2 metal organic
frameworks

Julianna Hajek a ,
Matthias Vandichel a ,
Ben Van de Voorde b ,
Bart Bueken b , Dirk De
Vos b , Michel Waroquier
a , Veronique Van
Speybroeck
10.1016/j.jcat.2015.08.015

Institution

Jilin University, Changchun, 130023,

China

Brookhaven National Laboratory,

Upton, New York 11973-5000, United
States

Slovak Academy of Sciences,

Dbravsk cesta 9, SK-84511
Bratislava, Slovak RepublicTohoku
University, Sendai 980-8577, Japan
Universitt Wien, Sensengasse 8/12,
A-1090 Wien, Austria

Ghent University, Technologiepark

914, 9052 Zwijnaarde, Belgium

University of Wisconsin-Madison, 1415

Engineering Drive, Madison, WI 53706,
USA

Simon Fraser University, Canada

Ghent University, Belgium

University of Leuven, Belgium

Abstract

The energetic results indicate that the most favorable pathway is the innersphere hydrogen transfer p
alkoxide complex [Pd(PhCH2O)(dppe)]+ (Int4i) and the catalytic cycle CC1. Initiation of Int4i includes
species [Pd(OH)(dppe)]+ and [Pd(PhNH)(dppe)]+ and (ii) PhCH2OH deprotonation with the aid of [Pd(
sequential steps: (i) -H elimination of Int4i to generate benzaldehyde and the Pd hydride species [Pd
the imine, and (iii) imine reduction to supply the amine product and to regenerate Int4i. The calculate
favorable, although it is inhibited by the reverse process of PhCH2OH deprotonation catalyzed by [Pd(
identify the TOF-determining intermediate (TDI) and the TOF-determining transition state (TDTS) in CC
LiCl2 -coordinated complexes in the overall reaction pathway, which leads us to conclude that LiCl2
that the TOF may be improved by the addition of AgOTf or AgBF4, which can scavenge the Cl and su

Here we report a high-surface-area Ag nanocoral catalyst, fabricated by an oxidationreduction metho

electro-reduction of CO2 to CO with a current efficiency of 95% at the low overpotential of 0.37 V and
and TON > 8.8 104 (over 72 h) was estimated for the Ag nanocoral catalyst at an overpotential of 0
enhancement in surface-areanormalized activity, at an overpotential of 0.49 V, as compared to Ag foil
adsorbed chloride anions play a critical role in the observed enhanced activity and selectivity of the A
ray photoelectron spectroscopy (XPS) studies along with a series of control experiments suggest that
under electrocatalytic conditions, can effectively inhibit the side reaction of hydrogen evolution and en

Following earlier suggestions we assume that the selectivity of MSR arises from the competition betwe
formaldehyde: the reaction of formaldehyde with hydroxyl leading ultimately to the formation of CO2,
production of CO. We have investigated whether the differences in the activation energies for these st
density-functional theory detailed atomistic scenarios for both reactions have been developed. As in v
it does not need the support of a catalyst to proceed. There is a clear correlation between high CO2 se
L10(1 1 1) surfaces we have to consider the existence of four inequivalent adsorption sites, caused by
tetragonal deformation of the L10 structure. At PtZn(1 1 1) this shift could explain the observed mixed
of selectivity can qualitatively explain the experimentally observed selectivities of the investigated int
understanding the influence of the ZnO support and the Zn-enriched PdZn surface on the selectivity o
selectivity of the catalyst are also presented

A fundamental kinetic model for the catalytic hydrogenation of benzene over Pt(1 1 1) has been const
optPBE vdW-DF functional. In contrast to traditional quantum chemical calculations at low to medium
hydrogen coverage of 0.44 in order to account for the strong lateral interactions between the surface
bar; pH2 = 0.56 bar; T = 400500 K). The destabilization of the surface species at increased hydroge
magnitude larger than at low hydrogen coverage, caused by not only reduced activation barriers, but
factors. Accounting for coverages representative for industrial conditions in the ab initio calculations is
the given methodology, the turnover frequency (TOF), temperature dependence of the TOF, and the p
agreement with experimental results.

Computational chemistry, especially density functional theory, has experienced a remarkable growth
to the improvements in theory and computing infrastructure that enable the analysis of systems of un
expense. In this perspective, we discuss recent progress and current challenges facing electronic struc
specifically focus on the impact of computational chemistry in elucidating and designing catalytic syst
synthesis, hydrotreating, and NOx reduction. We then discuss the common tools and concepts in comp
perspective on the challenges and future directions of research in this area of catalysis research.

Density functional theory was used to investigate the influence of the Pt adsorption state on the forma
two important reactive oxygen species. We generated the free energy diagrams of reduction sequenc
products. The Pt (111)water interface was considered in three adsorption states that are encountere
with a monolayer of hydrogen (low electrode potential); a clean surface (intermediate potential); and
potential). Results reveal a strong impact of surface water interactions on the pathways of water oxida
experimental results reported in the literature, we found that the oxygen reduction pathway is highly
hydrogen renders the surface highly hydrophobic, thereby suppressing its activity for the oxygen redu
H2O2 by a two-electron pathway becomes a preferred path. We discuss results in the context of radica
in polymer electrolyte fuel cells.

A full mechanistic investigation is proposed for the industrially important cross-aldol condensation rea
functionalized UiO-66-NH2 metalorganic frameworks to form jasminaldehyde. Several experimental s
can be increased by proper functionalization of the material, e.g. by introducing an additional basic am
aldol condensation. The precise molecular level origin for this behavior is to date unclear. Herein state
performed to unravel the mechanism of the cross- and self-aldol condensations of benzaldehyde and p
on both extended cluster and periodic models. It is found that the mechanism on both catalysts is ess
reactants and slightly lower barriers were found on the amino functionalized material, pointing toward
confirm these observations. It is indeed found that the initial activity toward cross-aldol condensation
40 min of reaction both materials become equally active. Our results furthermore point out that the ba
formation, which is induced by water. The study as presented can assist to engineer materials at the m