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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas, 78712, USA
Fuel Cell Research Center, Korea Institute of Science and Technology (KIST), Seoul, Korea
a r t i c l e
i n f o
Article history:
Received 2 May 2015
Received in revised form 15 July 2015
Accepted 30 July 2015
Available online 21 August 2015
Keywords:
AuPd(1 0 0)
Ensembles
ORR
First-principles
a b s t r a c t
Based on density functional theory calculations, we present that pairs of 1st nearest Pd monomers play an
important role in signicantly enhancing the oxygen reduction reaction (ORR) on the AuPd(1 0 0) surface.
While the catalytic ORR activity tends to be sensitive to the surface atomic ordering, we nd that the Pd
monomer pairs lead to a substantial reduction in the activation barrier for O/OH hydrogenation with no
signicant suppression of OO bond scission, thereby considerably lowering the overall activation energy
for the ORR as compared to the case of pure Pd(1 0 0). On the other hand, an isolated Pd monomer tends
to greatly suppress the OO bond cleavage reaction, which in turn slows down the ORR kinetics. Unlike
the monodentate adsorption of O2 on an isolated Pd monomer, the pairing of Pd monomers allows O2
adsorption in a bidentate conguration and consequently facilitating OO bond scission. However, the
barrier for OH hydrogenation at each Pd site shows no signicant change between the isolated and paired
cases, while it is noticeably lower than the pure Pd case.
2015 Elsevier B.V. All rights reserved.
1. Introduction
Bimetallic gold-palladium (AuPd) catalysts have been tested and
used for various chemical reactions such as production of vinyl
acetate monomer [1], low temperature oxidation of carbon monoxide [25], selective oxidation of formic acid [68], and selective
production of hydrogen peroxide (H2 O2 ) from molecular O2 and H2
[6,911]. Recent studies suggest that the surface activity of AuPd
is governed by the various alloying effects such as the so-called
electronic (ligand) effects [4,6,1215] (electronic state change by
metalmetal interactions) and ensemble (geometric) effects (modication of catalytic activity by the unique arrangement of surface
atoms) [1620]. However, the underlying mechanism of AuPd alloy
catalysis still remains unclear.
It has been theoretically and experimentally found that an isolated Pd monomer surrounded by Au atoms is a good site for
increasing the rate of O/OH hydrogenation reaction but signicantly slowing down the kinetics of O2 bond cleavage, thereby
yielding the signicant enhancement of selective H2 O2 formation
Corresponding author. Tel.: +82 2 958 5889; fax: +82 2 958 5199.
Corresponding author. Tel.: +1 512 471 4847; fax: +1 512 471 7060.
E-mail addresses: hchahm@kist.re.kr, ham.hyungchul@gmail.com (H.C. Ham),
gshwang@che.utexas.edu (G.S. Hwang).
http://dx.doi.org/10.1016/j.cattod.2015.07.054
0920-5861/ 2015 Elsevier B.V. All rights reserved.
12
Fig. 1. Tilted side view of the model PdAu surfaces considered in this work, an isolated Pd monomer (indicated by 1M), a pair of 1st nearest monomers (1st 2MP), a dimer (D),
a trimer (T), a tetramer (TE) and a Pd(1 0 0) slab (P). The green, gold, and gray balls represent surface Pd, surface Au, and subsurface Pd atoms, respectively. (For interpretation
of the color information in this gure legend, the reader is referred to the web version of the article.)
become smaller than 5 102 eV/. The lattice constant for bulk
which is virtually identical to previous
Pd is predicted to be 3.95 A,
DFT-GGA calculations and also in good agreement with the exper The binding energy (Eb ) of O2 is calculated
imental value of 3.89 A.
by Eb = E(M) + E(O2 ) E(O2 /M), where E(O2 /M), E(M), and E(O2 ) represent the total energies of the O2 /slab system, the bare slab, and
an isolated triplet O2 molecule in the gas state, respectively.
2. Computational methods
3. Results and discussion
The calculations reported herein were performed on the basis
of spin polarized DFT within the generalized gradient approximation (GGA-PW91) [32], as implemented in the Vienna Ab-initio
Simulation Package (VASP) [33]. The projector augmented wave
(PAW) method [34] with a plane-wave basis set was employed to
describe the interaction between core and valence electrons. The
valence congurations employed to construct the ionic pseudopotentials are: 5d10 6s1 for Au, 4d9 5s1 for Pd, and 2s2 2p4 for O. An
energy cut-off of 350 eV was applied for the planewave expansion
of the electronic eigenfunctions. For Brillouin zone sampling, we
used a (3 3 1) Monkhorst-Pack mesh of k points to determine
the optimal geometries and total energies of systems examined,
and increased the k-point mesh size up to (8 8 1) to re-evaluate
corresponding electronic structures. Reaction pathways and barriers were determined using the climbing-image nudged elastic
band method (c-NEBM) [35] with eight intermediate images for
each elementary step.
For a model surface, we used a supercell slab that consists of a
rectangular 4 4 surface unit cell with four atomic layers each of
which contains 16 atoms. For each AuPd surface model, the topmost
surface layer that is overlaid on a three-layer Pd (1 0 0) slab contains
selected Pd ensembles including an isolated Pd monomer (indicated by 1M), a pair of 1st nearest monomers (1st 2MP), a dimer
(D), a trimer (T), and a tetramer (TE) (see Fig. 1). A slab is separated from its periodic images in the vertical direction by a vacuum
space corresponding to seven atomic layers. While the bottom two
layers of the four-layer slab were xed at corresponding bulk positions, the upper two layers were fully relaxed using the conjugate
gradient method until residual forces on all the constituent atoms
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Table 1
Calculated formation energies (in eV) of various Pd ensembles on AuPd(1 0 0) surface. The green and yellow represent the Pd and Au atoms, respectively.
1M
1st 2MP
TE
0.39
0.39
0.42
0.42
0.43
Fig. 2. Predicted molecular congurations of the initial, transition and nal states
in the O-O bond scission and O/OH hydrogenation reactions at the 1st 2MP site. Red,
yellow, green, and white balls indicate O, Au, Pd, and H atoms, respectively. (For
interpretation of the color information in this gure legend, the reader is referred
to the web version of the article.)
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Table 2
Calculated total energy changes (E) and activation barriers (Ea in parenthesis) for O-O bond scission and O/OH hydrogenation reactions on various Pd ensembles with
respect to fully separated co-adsorbed species. The symbol P indicates the pure Pd(1 0 0) slab. The All energy values are given in eV.
(A) O2 (g) O2
(B) O2 O + O
(C) O + H OH
(D) OH + H H2 O(g)
1M
1st 2MP
Pt(1 1 1)
0.48 ()
0.02 (1.04)
1.40 (0.34)
0.67 (0.68)
0.60 ()
0.52 (0.48)
0.92 (0.48)
0.54 (0.63)
1.10 ()
0.54 (0.89)
0.83 (0.71)
0.05 (1.03)
1.73 ()
0.89 (0.15)
0.55 (0.54)
0.14 (0.95)
0.83 ()
1.77 (0.56)
0.00 (1.06)
0.30 (0.34)
Fig. 4. Local density of states projected onto the 2p orbital of O2 adsorbed on a single
Pd monomer (1M), a pair of 1st nearest monomers (1st 2MP), a dimer (D), a trimer
(T) and a pure Pd(1 0 0) (P). The 2p orbital of gas state O2 is also presented. The Fermi
level (Ef ) is marked by the vertical line.
for the Pd monomer pairs (1st 2MP), trimer (T) and pure Pd(1 0 0)
cases, the spin-up and spin-down states are nearly degenerate with
a magnetic moment of 0.02, indicating the formation of peroxolike O2 by completely lling the antibonding 2p orbital (g* ) of
adsorbed O2 by the charge transfer from the surface. Here, O2 is
preferentially adsorbed in the bridge-hollow-bridge (b-h-b) conguration. On the contrary, for the single Pd monomer and dimer
cases, we predict the signicant magnetic moment of 0.99 (1M)
and 0.50 (D), implying the superoxo-like character of the bound
O2 by partially lling antibonding 2p orbital (g* ) by less charge
transfer from surface than the 1st 2MP, T and P cases. Here, O2
is preferentially adsorbed in the top-bridge-top (t-b-t) conguration. This demonstrates that both Pd atoms in a pair of 1st nearest
monomers (1st 2MP) can play an key role in signicantly enhancing
the O2 activation on AuPd(1 0 0) surface.
3.3. O/OH hydrogenation
Looking at O/OH hydrogenation, our calculations predict very
noticeable enhancement in the kinetics on 1M (0.34/0.68 eV) and
1st 2MP (0.48/0.63 eV) when compared to the pure Pd(1 0 0) surface (0.54/0.95 eV), while the O/OH hydrogenation barriers tend
to increase on D (0.71/1.03 eV). This suggests that Pd monomers
in both 1M and 1st 2MP can contribute to facilitating the O/OH
hydrogenation reactions; that is, the monomer pair can behave
like an isolated monomer for O/OH hydrogenation. It would be also
interesting to note that the rate-limiting step on each ensemble
may change considering the signicant differences in the activation
barriers for the O2 scission and OH hydrogenation reactions.
First, we nd that for the Pd(1 0 0) surface the OH hydrogenation reaction is rate-limiting with a barrier of 0.95 eV, while for the
Pt(1 1 1) surface, the O hydrogenation reaction is rate-determining
step with a barrier of 1.06 eV, indicating the improved ORR kinetics
in Pd(1 0 0) over Pt(1 1 1). This agrees well with a recent experimental result where the ORR activity in Pd(1 0 0) is higher than Pt(1 1 1)
case [40].
Next, looking at Pd ensembles cases, we nd that the OH hydrogenation reaction is rate-limiting on 1st 2MP (Ea = 0.63 eV), and
D (1.03 eV), whereas the O2 scission reaction is on 1M (1.04 eV).
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