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The influence of residual Ag on the formation of stable ad- enced both the OSC and activity, with a more qualitative corre-
sorbed active oxygen species (oxygen storage capacity, OSC) lation for the fresh catalysts and an approximately linear rela-
and its correlation with the activity and stability in the CO oxi- tionship for the stable catalysts after 1000 min on stream. A
dation reaction on nanoporous gold (NPG) was investigated by strictly linear correlation between catalytic activity and OSC,
a combination of kinetic and temporal analyses of products both before and after the reaction, indicated that the active
(TAP) reactor measurements, comparing four different NPG oxygen detected by the TAP reactor measurements also repre-
samples with different Ag contents. The data demonstrated sents the active oxygen species for the reaction at atmospheric
that oxygen can be activated and stored on the NPG catalysts pressure. Consequences for the mechanistic understanding of
at room temperature. Clearly the surface Ag content influ- the CO oxidation reaction on NPG catalysts are discussed.
Introduction
Oxide supported Au catalysts with Au nanoparticles of a few high activity for CO oxidation.[13–18] Since there is no support
nanometers in diameter have been the subject of numerous material in these samples, this seems to indicate that interac-
studies,[1] most prominently, on the CO oxidation reaction,[1–3] tions between the metal oxide support and the gold nanopar-
since the early reports by Haruta et al. about their high activity ticles and the resulting interface sites are not a prerequisite for
in various oxidation and reduction reactions at low tempera- highly active Au catalysts.[14, 15] Based on the results of detailed
tures.[4] The physical origin of their high activity as well as the reaction kinetic measurements, Wittstock et al. recently sug-
underlying mechanisms are still under debate, but in most gested that the residual Ag on the surface of NPG catalysts
mechanistic proposals, the oxide support and the interface be- plays a significant role in activating molecular oxygen and that
tween the supporting oxide and a Au nanoparticle play major these NPG catalysts should be considered as a bimetallic cata-
roles.[1, 5] For oxidation reactions, including CO oxidation, the lyst rather than as a pure Au catalyst.[19] In a recent TAP reactor
adsorption and activation of O2 is the decisive step and is study, we found NPG catalysts to be active for continuous CO
most intensely debated. Open questions include the nature of oxidation at atmospheric pressure for over 1000 min on stream
the active adsorbed oxygen species, where molecular or in a micro-reactor but with no measurable catalytic activity
atomic species are possible, and of the active site for oxygen during simultaneous pulsing of CO and O2 under vacuum con-
activation and its location on the catalyst, for example on the ditions in the TAP reactor.[20] Multipulse TAP experiments and
Au particle, on the surface of the oxide support or at the pe- temperature programmed desorption (TPD) spectra recorded
rimeter of the interface between the two. In recent quantita- after reactions with labeled 18O2 revealed that molecular O2
tive measurements in a temporal analysis of products (TAP) re- can be activated, most likely in atomic form, and stored on the
actor, we demonstrated that on various oxide supported Au NPG catalyst, but with very low efficiencies,[20] much lower
catalysts active oxygen species can be reversibly stored and re- than observed on Au/TiO2 catalysts.[8–10] While these measure-
actively removed upon alternating exposure to O2 and CO ments provided clear proof for the ability of the NPG catalyst
pulses and that the active oxygen species is most likely surface
lattice oxygen at the perimeter of the interface between the [a] Dr. L. C. Wang, D. Widmann, Prof. Dr. R. J. Behm
Au nanoparticle and the oxide support.[6–9] Furthermore, for Universitt Ulm, Institut fr Oberflchenchemie und Katalyse
Albert-Einstein-Allee 47, 89069 Ulm (Germany)
Au/TiO2, both the oxygen storage capacity (OSC) and the reac-
Fax: (+ 49) 731-5025452
tivity of the Au/TiO2 catalyst showed an almost linear relation- E-mail: juergen.behm@uni-ulm.de
ship with the perimeter of the interface between the Au nano- [b] Y. Zhong, Prof. Dr. J. Weissmller
particles and the TiO2 support, providing the first direct sup- TU Hamburg-Harburg
port for the proposed mechanism of the reaction occurring at Institut fr Werkstoffphysik und Werkstofftechnologie
Eißendorfer Straße 42
perimeter sites.[10]
21073 Hamburg (Germany)
In the last few years, it has been shown, however, that mon-
[c] Y. Zhong, Prof. Dr. J. Weissmller
olithic nanoporous gold (NPG), prepared by the selective disso- Helmholtz-Zentrum Geesthacht, Institut fr Werkstoffforschung
lution of Ag from a AuAg alloy,[11, 12] also exhibits a remarkably Max-Planck-Straße 1, 21502 Geesthacht (Germany)
ChemCatChem 2012, 4, 251 – 259 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 251
R. J. Behm et al.
252 www.chemcatchem.org 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2012, 4, 251 – 259
CO Oxidation
ChemCatChem 2012, 4, 251 – 259 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemcatchem.org 253
R. J. Behm et al.
It should be mentioned that after reaction for 1000 min, the catalyst by integrating the CO2 signal intensities and summing
surface areas of the four NPG catalysts are much closer to each up over all of the pulses.
other than before, indicating a much more pronounced coars- From the raw data presented in Figure 3 (note that for
ening of the samples with initially smaller ligaments (NPG-2 – better resolutions only the first 20 pulses are shown), it is obvi-
NPG-4). These results clearly show the changing structure of ous that the different samples investigated vary significantly in
the NPG in the reaction atmosphere, in agreement with previ- their OSC, with NPG-1 having the lowest and NPG-4 having
ous reports, even on a quantitative scale.[14] The number of Ag the highest OSC, while NPG-2 and NPG-3 have intermediate
atoms present on the catalyst surface after the reaction was OSC values. For the fresh samples (OSC-1), the corresponding
also calculated and is included in Table 1 for comparison with absolute values are 0.04, 1.4, 0.63, and 2.1 1019 O atoms gAu 1
the data obtained from the fresh samples. for NPG-1, NPG-2, NPG-3, and NPG-4, respectively (Table 2). We
also measured the OSC of each catalyst after exposure to reac-
tion conditions for 1000 min in the TAP reactor (OSC-2); the re-
Oxygen storage capacity
sulting values are 0.03, 1.2, 0.54, and 0.86 1019 O atoms gAu 1
The amount of active oxygen adsorbed stably onto the catalyst for the NPG-1, NPG-2, NPG-3, and NPG-4 catalysts, respectively
surface after exposure to O2/N2 at atmospheric pressure was (Table 2). Whereas NPG-1 to NPG-3 showed only moderate de-
determined by titration with CO/Ar pulses under reduced pres- creases in the OSC, this decrease was much larger for NPG-4.
sure as described in the Experimental Section. Figure 3 shows In Figure 4, we present the plot of the OSC values of the dif-
the intensities measured for the product (CO2) which resulted ferent catalysts against the total number of Ag atoms present
from the titration of stable adsorbed, active oxygen by CO for on the catalyst surface before and after reaction. Starting with
all four samples after the same pretreatment in oxygen (in situ the fresh catalysts (OSC-1), there is obviously a qualitative cor-
relation between these two quantities, but the devi-
ations from a linear correlation are significant, in par-
ticular for the catalysts NPG-2 and NPG-3. For the
stable catalysts (OSC-2), after 1000 min on stream,
this linear correlation is much better fulfilled, al-
though with a considerably higher slope than ob-
tained for the fresh catalysts. Obviously, after the re-
action, structural and other differences between the
catalysts have decreased; therefore, the number of
Ag surface atoms becomes more decisive. Compari-
son of the OSC values with the surface areas
(Table 1) does not reveal any reasonable correlation,
indicating that contributions arising from different
surface areas are less important. They may still be
significant, but are covered by other effects such as
the content of Ag surface atoms.
We tentatively propose that adsorption and acti-
vation of oxygen takes place at sites which are con-
Figure 3. CO2 signals measured during CO/Ar pulses at 30 8C over the various NPG cata- nected to surface Ag atoms, occurring either directly
lysts after exposure to 10 % O2 in N2 (20 N ml min 1) at atmospheric pressure
for 30 min at 30 8C. a) NPG-1, b) NPG-2, c) NPG-3, and d) NPG-4.
Table 2. Oxygen storage capacity (OSC) and catalytic activity for CO oxi-
exposure to a gas mixture containing 10 % O2 in N2 for 30 min dation at 30 8C for various NPG catalysts.
at atmospheric pressure). Note that the conversion of CO mol- Catalyst NPG-1 NPG-2 NPG-3 NPG-4
ecules reached up to 100 % during the first few pulses and
OSC-1 [1019 O atoms gAu 1][a] 0.04 1.4 0.63 2.1
subsequently decreased exponentially until further uptake of
OSC-2 [1019 O atoms gAu 1][b] 0.03 1.2 0.54 0.86
CO could no longer be detected (Figure 3). At the beginning initial rAu [10 5 mol s 1 gAu 1][c] 0.4 12.4 3.4 18.2
of the CO pulses, the reaction could be limited by diffusion of stable rAu [10 5 mol s 1 gAu 1][d] 0.3 9.2 3.6 6.2
CO into the pore structure. However, since the OSC is an accu- dry rAu [10 5 mol s 1 gAu 1][d,e] – 7.5 2.5 3.7
initial TOF (Au) [s 1] 0.02 0.1 0.03 0.1
mulative quantity, which is not affected by the reaction kinet-
stable TOF (Au) [s 1] 0.03 0.6 0.3 0.4
ics, mass-transport limitations do not play a role for the deter- initial TOF (Ag) [s 1] 0.4/0.4[f] 1.1/2.2[f] 0.3/0.4[f] 0.6/0.9[f]
mination of the OSC. It only depends on the total amount of stable TOF (Ag) [s 1] 0.1[f] 1.5[f] 0.8[f] 1.2[f]
active sites for O2 activation on the surface of the catalyst. [a] OSC obtained before 1000 min on stream. [b] OSC obtained after
Since the amount of CO2 formed by titration with CO equals 1000 min on stream. [c] initial reaction rate. [d] stable reaction rate mea-
the amount of (atomic) oxygen stored on the surface of the sured after 1000 min on stream. [e] reaction rate measured after drying
pretreatment. [f] TOF based on surface areas calculated from the ligament
catalyst, one can obtain the OSC of the corresponding NPG
sizes.
254 www.chemcatchem.org 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2012, 4, 251 – 259
CO Oxidation
Figure 4. OSC of the NPG catalysts at 30 8C plotted against the total amount
of surface Ag atoms gcat 1 (NAg) of the different NPG catalysts before reaction
(OSC-1, empty columns) and after 1000 min on stream (OSC-2, filled col-
umns). Error margins are below 5 % of the respective OSC.
ChemCatChem 2012, 4, 251 – 259 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemcatchem.org 255
R. J. Behm et al.
all of the catalysts and over the entire time of the experiment
(Figure 6, Table 2). The characteristic behavior of the temporal
evolution of the activity with time on stream, however, is main-
tained (Figure 6). Again for NPG-4, the activity decays continu-
Figure 7. Initial (empty columns) and stable (filled columns) activities of the
NPG catalysts measured in a microreactor at 30 8C plotted against the OSC
measured by CO titration after exposure to 20 N ml min 1 10 % O2 in N2 for
30 min at 30 8C before (OSC-1, empty columns) and after (OSC-2, filled col-
umns) the reaction.
Figure 6. Mass normalized reaction rates of the NPG catalysts with different
Ag contents measured in a microreactor under different reaction conditions represents the active site for CO oxidation, one would expect
as a function of reaction time after drying in a flow of N2 at 30 8C for 16 h
(reaction temperature 30 8C, 60 N ml min 1: 1 % CO, 1 % O2, rest N2, atmos- comparable TOF numbers for all of the catalysts. The total
pheric pressure). number of Au surface atoms was calculated in the same way
as described before for the calculation of Ag surface atoms.
For initial activities, the resulting TOF numbers based on Au
ously, but for the other two samples it passes through a maxi- surface atoms are 0.02, 0.1, 0.03, and 0.1 s 1 for the catalysts
mum (NPG-2) or approaches its maximum value (NPG-3). In NPG-1–NPG-4, respectively, and based on Ag surface atoms,
combination, these findings clearly indicate that there is a dis- the corresponding TOF numbers are 0.4, 1.1, 0.3, and 0.6 s 1,
tinct difference from the reaction measurements on the sam- respectively. After 1000 min on stream, the corresponding
ples without the drying pretreatment. Despite these differen- values are 0.03, 0.6, 0.3, and 0.4 s 1 (Au) and 0.1, 1.5, 0.8 and
ces, it is clear from these results, however, that the significantly 1.2 s 1 (Ag), respectively. Obviously, this normalization does not
higher activity of sample NPG-2 or the different deactivation result in constant TOF numbers, neither for Au nor for Ag sur-
behavior of sample NPG-4 cannot be related to the effect of face atoms, indicating that neither the Au nor the Ag surface
water because similar behaviors were found for the dried atoms alone can account for the CO oxidation activities of the
samples. NPG catalysts without taking other factors into consideration.
Finally, we plotted the catalytic activities, given by the initial Here it should be noted that, as briefly mentioned before,
and stable (Au mass based) reaction rates after 1000 min reac- there is some discrepancy between surface areas measured di-
tion, versus the total amount of active oxygen (per gAu) that rectly and those calculated from the ligament sizes, which is
can be stored on the catalyst surface, as detected by multi- also carried over to the TOF numbers. These differences, how-
pulse TAP experiments before and after the reaction (Table 2). ever, are by far too small to explain the observed differences in
As shown in Figure 7, the data excellently fit a linear relation TOF numbers between the different catalysts for both Au and
between reaction rate and OSC both before and after the reac- Ag based TOF numbers. Furthermore, they should not affect
tion. This clearly proves that the adsorbed active oxygen spe- the numbers derived for the initial activity. The scatter in Ag
cies, which were titrated by CO/Ar pulses in the TAP reactor based TOF numbers directly reflects the deviation from a linear
measurements, also act as active species under realistic reac- relation between activity and number of Ag surface atoms per
tion conditions at atmospheric pressure, closely resembling gram of catalyst.
our previous findings for different oxide supported Au cata- Improved catalytic properties were also reported for oxide
lysts.[6, 8–10] Taking into account the almost linear relationship supported catalysts. Studying CO oxidation on a series of
between OSC and surface Ag atoms, at least after the reaction, AuAg alloy catalysts supported on mesoporous aluminosilicate,
this result also indicates that Ag surface atoms represent or at Wang et al. reported a pronounced effect of the composi-
least are part of the active sites for both O2 activation and the tion.[22] The best performing AuAg alloy catalyst was found to
CO oxidation reaction under stable conditions. be the one with a bulk Au/Ag ratio of 3:1, in which the surface
To remove the effect of the different surface areas in the composition varied significantly due to Ag surface segregation.
comparison of the different activities, we also calculated turn- Similar results were also reported by Sandoval et al. for AuAg
over frequencies from both the initial and steady-state activi- bimetallic catalysts supported on TiO2, with a Au/Ag ratio of
ties of the different NPG catalysts based on the number of 1:0.37 showing the highest catalytic activity.[28] Density func-
either Au surface atoms or Ag surface atoms. If either of them tional theory calculations showed that CO and O2 coadsorption
256 www.chemcatchem.org 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2012, 4, 251 – 259
CO Oxidation
on neighboring sites on the AuAg alloy was stronger than that From the absence of a clear correlation between the activity
on either Au or Ag, which contribute to the observed syner- for CO oxidation and the catalyst surface area, we conclude
getic effects in the catalytic performance.[29, 30] Finally, consider- that the surface area does not play a dominant role in the ac-
ing the decisive role of O2 activation in Au catalyzed oxidation tivity of these surface Ag containing samples. The same is true
reactions, the findings by Kondarides and Verykios[31] are partic- for the OSC. Due to the preparation procedure, however, a
ularly interesting. They claimed that atomically adsorbed change in surface Ag content is often, but not necessarily, cor-
oxygen is favored for higher concentrations of surface Ag related with a change in surface area.
atoms, but for lower concentrations, molecularly adsorbed spe- Overall, we could clearly demonstrate that active oxygen is
cies are favored. In total, these results demonstrate that the adsorbed stably onto the surfaces of Au NPG catalysts and
presence of Ag has a significant impact on the catalytic activity that the species detected in the TAP reactor is also the active
of Au catalysts in general, although a detailed understanding species for the reaction at atmospheric pressure. These active
of the physical origin is still missing. sites are related to the presence of surface Ag; however, their
actual nature has not yet been resolved.
ChemCatChem 2012, 4, 251 – 259 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemcatchem.org 257
R. J. Behm et al.
spectra were recorded on the NPG powders using a PHI 5800 ESCA was 60 N ml min 1 (1 % CO, 1 % O2, rest N2). The resulting CO:O2
system (Physical Electronics) with monochromatic AlKa radiation. ratio was 1:1 and, hence, there was an excess of oxygen relative to
The Ag surface concentrations were calculated from the measured stoichiometric reaction conditions. Both influent and effluent gases
intensities of the Ag (3d) signals using tabulated sensitivity factors, were analyzed by on-line gas chromatography (DANI, GC 86.10).
which assumed constant composition of the topmost layers. For further details on the set-up and the evaluation see ref. [37].
258 www.chemcatchem.org 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2012, 4, 251 – 259
CO Oxidation
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[28] A. Sandoval, A. Aguilar, C. Louis, A. Traverse, R. Zanella, J. Catal. 2011, [34] S. Trasatti, O. A. Petrii, Pure Appl. Chem. 1991, 63, 711 – 734.
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[29] A.-Q. Wang, C.-M. Chang, C.-Y. Mou, J. Phys. Chem. B 2005, 109, 18860 – Sci. Instrum. 2007, 78, 104103 – 1 – 104103 – 9.
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[30] C.-W. Yen, M.-L. Lin, A. Wang, S.-A. Chen, J.-M. Chen, C.-Y. Mou, J. Phys. A 1997, 160, 55 – 88.
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[32] S. Parida, D. Kramer, C. A. Volkert, H. Rçsner, J. Erlebacher, J. Weissml- Received: August 25, 2011
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ChemCatChem 2012, 4, 251 – 259 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemcatchem.org 259