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DOI: 10.1002/cctc.

201100297

On the Role of Residual Ag in Nanoporous Au Catalysts for


CO Oxidation: A Combined Microreactor and TAP Reactor
Study
L. C. Wang,[a] Y. Zhong,[b, c] D. Widmann,[a] J. Weissmller,[b, c] and R. J. Behm*[a]

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.

to activate O2 adsorption at 30 8C, they did not give informa-


tion on the nature of the active sites for the activation of mo-
lecular O2 and on the role of Ag in the oxygen activation
process.
This is the topic of the present paper, in which we report re-
sults of a comparative TAP reactor and a reaction kinetic study
on the OSC and on the CO oxidation activities of four different
NPG catalysts with different residual Ag contents. These were
prepared by applying different voltages in the electrochemical
dealloying step or during a subsequent cleaning procedure.
For a detailed discussion of the impact of the corrosion condi-
tions on the Ag retention see ref. [21]. The morphology, struc-
ture, and chemical composition of the resulting catalysts were
characterized by scanning electron microscopy (SEM), powder
X-ray diffraction (XRD), and X-ray photoelectron spectroscopy
(XPS). The amount of active oxygen species on the catalysts
(OSC) was determined by titration experiments performed in a Figure 1. SEM images of NPG catalysts before and after 1000 min on stream.
TAP reactor after exposure of the samples to an O2/N2 gas flow a) NPG-2 before reaction, b) NPG-2 after reaction, c) NPG-4 before reaction,
at atmospheric pressure. These measurements were performed d) NPG-4 after reaction. Scale bars = 0.5 mm.

on the fresh NPG samples (before reaction) as well as on sam-


ples after CO oxidation under atmospheric pressure for
Table 1. Details on the preparation and physical properties for various
1000 min. The CO oxidation activities of the catalysts were de-
NPG catalysts.[a]
termined in a conventional microreactor at atmospheric pres-
sure. SEM and XRD measurements on the NPG catalyst, per- Catalyst NPG-1 NPG-2 NPG-3 NPG-4
formed after the activity measurements, allowed us to gain fur- potential during 1.280 1.330 1.380 1.380
ther insights into the structural stability of the NPG catalysts. dealloying [VSHE]
The correlations between the OSC, CO oxidation activity, and potential during 1.530 1.530 1.530 1.480
cleaning procedure [VSHE]
Ag content or surface area and their consequences on the average crystallite 20.7 (28.0) 6.4 (20.6) 4.1 (23.2) 4.1 (21.0)
nature of the active sites as well as on the role of residual Ag size D [nm][b]
in the oxygen activation step during CO oxidation on NPG cat- surface area  10 63 59 75
alysts are discussed. [m2 g 1][c]
surface area estimated 10 (7) 31 (10) 51 (9) 50 (10)
from D [m2 g 1][d]
bulk Ag 4.5 13.2 14.4 14.6
Results and Discussion [at. %][e]
Catalyst characterization surface Ag 5.4 (16.6) 9.5 (30.0) 10.5 (24.7) 18.6 (25.3)
[at. %][f]
As-prepared catalysts amount of surface 1.1 6.6 6.1 7.1
Au atoms [1020 gcat 1]
Figure 1 shows representative SEM images of the samples amount of surface 0.06 (0.13) 0.69 (0.34) 0.71 (0.26) 1.6 (0.29)
NPG-2 and NPG-4 (Figure 1 a and b, c and d, respectively). Prior Ag atoms [1020 gcat 1]
to the reaction, both of the samples showed spongelike mor- [a] the data presented in parentheses were obtained from the samples
phologies with ligament diameters below 10 nm (Figures 1 a after 1000 min on stream. [b] estimated from Au(111) diffraction peaks by
using the Scherrer equation. [c] surface areas of the fresh samples mea-
and c). The limited resolution of the SEM images prevented
sured by capacitance ratio method. [d] estimated by assuming idealized,
quantification of the rather small ligament sizes; therefore, cylindrical ligaments with diameter D. [e] measured by SEM-EDX. [f] deter-
XRD measurements were performed on these samples to gain mined by XPS.
further information on the structural properties of the bulk
phase. As shown in Figure 2, the three samples, NPG-2 – NPG-
4, exhibited broad diffraction peaks of metallic Au, indicating in the NPG samples increased, with a sharp increase when
that the crystallite sizes of the fresh samples are very small. On going from 1.280 VSHE (4.5 at. % Ag, NPG-1; SHE = standard hy-
NPG-1, the diffraction peaks are significantly sharper. Using the drogen electrode) to 1.330 VSHE (13.2 at. % Ag, NPG-2) and a
Scherrer equation, the mean crystallite sizes of the samples rather low increase when further raising the potential to
NPG-1, NPG-2, NPG-3, and NPG-4 were determined to 20.7, 6.4, 1.380 VSHE (14.4 at. % Ag and 14.6 at. % Ag for catalysts NPG-3
4.1 and 4.1 nm, respectively (Table 1). and NPG-4, respectively). For the samples NPG-1, NPG-2, and
The physical properties and chemical composition of the NPG-3, which after dealloying were cleaned at a potential of
four different NPG samples, including the bulk (EDX) and sur- 1.530 VSHE, the surface Ag content follows the same trend with
face (XPS) Ag content and the specific surface area (capaci- slight variations compared to the bulk Ag content (5.4, 9.5,
tance ratio measurements), are summarized in Table 1. With in- and 10.5 at. % Ag for NPG-1, NPG-2, and NPG-3, respectively;
creasing potential for dealloying, the residual (bulk) Ag content Table 1). In contrast, the catalyst NPG-4 showed a significantly

252 www.chemcatchem.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2012, 4, 251 – 259
CO Oxidation

values[21] reports a continuous decrease of bulk Ag retention


— prior to cleaning — with increasing potential for acidic elec-
trolytes. The present data confirm that by varying the dealloy-
ing potential and the subsequent cleaning procedure, it is pos-
sible to obtain samples with significantly different surface Ag
content. Empirically, we found that higher cleaning potentials
provide a slightly more efficient removal of surface Ag.

Catalysts after the reaction


To identify and quantify possible structural changes during the
activity measurements, the NPG catalysts were retrieved after
the reactions and subsequently recharacterized. The SEM re-
sults indicated a coarsening of the porous surface structure
upon exposure to the reaction mixture, as can be seen in Fig-
ure 1 b and d. The XRD patterns presented in Figure 2 b re-
vealed a significant sharpening of the diffraction peaks for all
four samples upon reaction, pointing to a pronounced coars-
ening also of the bulk structure, yielding crystallite sizes of
28.0, 20.6, 23.2 and 21.0 nm for NPG-1–NPG-4 after reaction, re-
spectively. Note that, in addition to the Bragg reflections of Au,
sharp peaks in the XRD patterns after the reaction characteris-
Figure 2. XRD patterns of various NPG catalysts a) before and b) after
1000 min on stream. tic of SiO2, which was used as a dilution material during the re-
action, can also be identified. A similar observation of a reac-
tion induced increase of the ligament size of nanoporous gold
higher surface Ag content (18.6 at. %), although its bulk Ag upon exposure to a CO oxidation reaction mixture (25 h, 30 8C)
concentration is comparable to that of the NPG-3 sample. We was reported by Xu et al.[14]
tentatively attribute this difference to the lower potential used The surface areas and chemical surface compositions of vari-
during the cleaning procedure for the NPG-4 sample. ous NPG catalysts after reaction are summarized in Table 1.
Parallel to the increased Ag content (bulk and surface) of Due to the very low amounts of NPG catalyst used during the
the samples with increased dealloying potential, the surface reaction (2 mg) and the fact that we pulverized the samples, it
area also increased sharply when going from 1.280 VSHE to was not possible to measure the surface area of the samples
1.330 VSHE, from  10 m2 gcat 1 for NPG-1 to 63 m2 gcat 1 for after reaction by the capacitance ratio method, as was done
NPG-2, but a further increase to 1.380 VSHE showed no distinct for the fresh samples. Therefore, the surface areas of the used
effect (59 m2 gcat 1 for NPG-3 and 75 m2 gcat 1 for NPG-4). For NPG catalysts were estimated by assuming idealized, cylindrical
comparison, the surface areas of the fresh NPG samples were ligaments with a diameter D on the basis of the XRD results, as
also estimated from the crystallite size, assuming idealized, cy- described above. Here, we should keep in mind the deviations
lindrical ligaments with a diameter given by the crystallite size between the initial surface areas determined directly (capaci-
D. Although the results for the samples NPG-1 (10 m2 gcat 1) tance ratio method) and those using the ligament size men-
and NPG-3 (51 m2 gcat 1) are comparable to the data measured tioned above. Similar discrepancies are also expected for the
by the capacitance ratio method, the surface areas were lower final surface areas after the reaction. This is important to real-
than those measured for the NPG-2 (31 versus 63 m2 gcat 1) and ize because it will affect the number of Ag (Au) surface atoms
NPG-4 (50 versus 75 m2 gcat 1) samples. These results point to per gram of catalyst and, hence, the turn over frequency (TOF)
significant deviations of the real ligament shape from the ideal numbers calculated from these quantities. For all four NPG
cylindrical model. We also calculated the total amount of Ag samples, the reaction led to a pronounced enrichment of Ag
atoms present on the catalyst surface per gram of catalyst (for on the surface, with NPG-1 and NPG-2 having the lowest and
the relative amount of Ag at the surface see Table 1) to correct highest surface Ag content (16.6 at. % for NPG-1 and 30.0 at. %
for differences/changes in the Ag surface content. The total for NPG-2); intermediate surface Ag contents were obtained
amount of Ag atoms present on the surface was calculated by for NPG-3 (24.7 at. %) and NPG-4 (25.3 at. %). Surface enrich-
multiplying the surface Ag content with the total number of ment of Ag in bimetallic AuAg systems has previously been
surface atoms (calculated by the surface area and assuming detected both experimentally[22] and theoretically (density
1.15  1015 atoms cm 2). Note that this approach assumes a ho- functional calculations).[23] The driving force for the observed
mogeneous, vertical distribution of the Ag atoms in the surface surface segregation is the difference between the thermody-
regime analyzed by XPS. The resulting values are listed in namic properties of Au and Ag, especially the lower surface
Table 1. energy of Ag compared to Au.[24] The extent of Ag enrichment
We note that a recent study of Ag retention during electro- on the surface of AuAg alloys depends on temperature, com-
chemical dealloying of AgAu in media with various pH position, and particle size.[24]

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.

on surface Ag atoms or on ensembles for O2 adsorption includ-


ing surface Ag atoms. A more detailed picture of the activation
process or the active site cannot be derived from these data. Figure 5. a) Mass normalized reaction rates and b) relative activity, normal-
ized to the initial activity, of the NPG catalysts with different Ag contents
measured in a microreactor under differential reaction conditions as a func-
tion of reaction time (reaction temperature 30 8C, 60 N ml min 1: 1 % CO,
Catalytic activities
1 % O2, rest N2, atmospheric pressure).
To test for a direct correlation between the OSC and the cata-
lytic activity of the NPG samples for CO oxidation, which was
observed for Au/TiO2[10] and other oxide supported Au cata- tivity measurements were performed under differential reac-
lysts,[9] we determined the CO oxidation activity of the four tion conditions, with conversions below 20 % for CO and O2
NPG catalysts and the CO2 development with time on stream during the reaction. Therefore, the influence of mass transport
in a standard reaction mixture (1 % CO, 1 % O2, rest N2) at at- phenomena on the measured reaction rates is not significant
mospheric pressure and 30 8C. The results of the activity meas- and cannot explain the differences in the activities among the
urements are presented in Figure 5. The NPG-4 catalyst, which different catalysts.
was also investigated in our previous study, exhibited the high- Similar to our findings, Wittstock et al. also reported an acti-
est initial activity (1.8  10 4 molCO s 1 gAu 1) among the four cat- vation period of approximately 2–3 h at 80 8C when conduct-
alysts and showed a reaction behavior typical for CO oxidation ing catalytic measurements on a NPG disk catalyst with a liga-
on supported Au/TiO2 catalysts,[25, 26] with an initial rapid decay ment size of 30–50 nm.[16] In fact, in their study, the pristine
of the activity for 200 min by about 60 % and then an almost NPG catalysts were not active for CO oxidation at room tem-
constant activity up to 1000 min on stream. In contrast, the perature.[16] They found that the activity then increased over
other three NPG catalysts featured a distinctly different reac- the next few hours, finally reaching either a plateau or, more
tion behavior, with an initial steady increase of the activity for often, passing through an activity maximum after which the
2–3 h, followed by a gradual decay by 20–30 % (Figure 5 b). CO2 production decreased again.[16] The authors postulated
The resulting steady-state activities, after 1000 min on stream, that the activation phase may be induced by the removal of
are 0.3, 9.2, 3.6, and 6.2  10 5 molCO s 1 gAu 1 for NPG-1–NPG-4, moisture adsorbed in the pores or contaminants stemming
respectively (Table 2). Interestingly, NPG-2 reproducibly showed from the leaching process.
a distinctly higher activity than NPG-3 and NPG-4, despite the To test whether such effects play a role also in the present
comparable surface areas and the higher number of surface study, we performed similar reaction measurements using cata-
Ag atoms in sample NPG-4. In a recent study, Wittstock et al.[16] lysts which were dried before the reaction measurements. For
demonstrated that mass transport limitations in the nanopo- supported Au catalysts, the presence of water on the catalyst
rous Au material may notably affect the measured kinetics, in- surface is known to enhance the CO oxidation activity, at least
cluding activity, reaction order, and activation energy. In their up to a critical water content.[27] In order to start with compa-
studies, however, the catalytic measurements were conducted rable water contents, samples are often subjected to a drying
using a NPG disk in a specially designed continuous flow reac- pretreatment before the reaction, like that recently reported
tor, but in our measurements, diluted powder NPG samples for Au/TiO2 catalysts.[26] After drying the samples (NPG-2,
were used (see the Experimental Section). An estimate of the NPG-3, and NPG-4) for 16 h in a flow of pure N2 passed
Thiele modulus yielded significantly lower values of < 3 than through a water filter at 30 8C and using dried reaction gases
derived in the study by Wittstock et al.[16] Furthermore, our ac- by passing them through a water filter, the rates are lower for

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.

Conclusions Experimental Section


Based on a combination of static and transient reaction meas- Nanoporous gold sample preparation
urements, performed in a conventional microreactor and in a
Nanoporous gold samples were prepared by electrochemical etch-
TAP reactor, respectively, on a series of four samples with dif- ing (dealloying) of an AgAu alloy, as reported previously.[32, 33] The
ferent (surface) Ag contents, we arrived at the following main master alloy Ag75Au25 (at. %) was prepared by the arc melting of
results and conclusions on the mechanism of the CO oxidation high purity Au and Ag wires (Au 99.9985 % and Ag 99.99 %, Chem-
reaction on nanoporous Au and the effect of residual Ag pres- pur) and subsequent homogenization at 950 8C for 70 h (sealed in
ent on the surface. a quartz tube). The ingots were rolled to form disks 0.5 mm thick
We found a distinct deactivation of the catalyst during the and were annealed at 500 8C for two hours in a vacuum for recov-
reaction (Figure 5), which goes along with a significant loss of ery. Dealloying was performed in an aqueous solution of HClO4
(1 m) with potentiostatic control. To obtain samples with different
surface area and a (relative) enrichment of Ag surface atoms.
amounts of residual Ag, different potentials were applied for the
Although qualitatively this relation is obvious, a quantitative dealloying procedure: 1.280 VSHE (NPG-1), 1.330 VSHE (NPG-2), and
relationship with any of these values, (total) surface area or the 1.380 VSHE (NPG-3 and NPG-4) with respect to a pseudo Ag/AgCl
number of Ag surface atoms, was not possible. We interpreted reference electrode (in 1 m HClO4). All of the potentials, however,
this as an indication of a more complex combination of these are quoted versus a standard hydrogen electrode (SHE), the poten-
two effects being responsible for the deactivation. Similar rela- tial of which is 0.53 V lower than that of the Ag/AgCl electrode.
tionships are observed for the OSC. Dealloying was stopped when the current fell to 10 mA. After deal-
There is a distinct linear relationship between the catalytic loying, the electrolyte was replaced by a new base electrolyte, and
a higher potential (either 1.530 VSHE for NPG-1, NPG-2, and NPG-3
activity and OSC for both the fresh and used NPG samples
or 1.480 VSHE for NPG-4) was applied to the sample for about one
(Figure 7). This confirms that, similar to findings for oxide sup- hour to further remove the Ag (ions) which had remained in the
ported Au catalysts, the active adsorbed oxygen detected on pore channels (Table 1). Subsequently, the nanoporous gold sam-
the NPG catalysts in the TAP measurements is also the active ples were repeatedly rinsed with pure water for cleaning. The NPG
species during CO oxidation under realistic reaction conditions disks were dried, crushed, and gently ground into a powder before
at atmospheric pressure. Both are affected in a similar way by use.
changes in the Ag surface concentration and in the surface
area. Catalyst characterization
Both the activity for CO oxidation (Table 2) and the amount
of active oxygen adsorbed on the NPG samples (Figure 4) Since the microstructure of the NPG samples would be destroyed
show approximate linearity with the number of surface Ag under the normal conditions of a BET measurement, the surface
areas of the as-prepared NPG materials were determined using the
atoms in the stable state, after the reaction. With the fresh
capacitance ratio method.[34] The surface areas of the NPG samples
samples, in contrast, such a relation was not obvious, at least after reaction (a) were estimated by assuming idealized, cylindrical
not for all of the samples. Obviously, the Ag surface content ligaments with diameter D (the average crystallite size from XRD
plays an important role in the activity for CO oxidation, but it results) using the relation a = 4/1D,[33] in which 1 is the mass densi-
is not the only decisive parameter. This is reflected also by the ty of gold (19.32 g cm 3). The surface morphology and microstruc-
variation in TOF numbers based on surface Ag atoms, both be- ture and the bulk concentration of Ag were determined by scan-
tween the different catalysts and before and after the reaction. ning electron microscopy (SEM) and energy dispersive X-ray spec-
Accordingly, Ag surface atoms are in some way involved in the troscopy (EDX), respectively. XRD measurements were performed
on a PANalytical MPD PRO instrument, using CuKa radiation (l =
reaction, for example by providing sites for the adsorption and
0.154 nm). The average crystallite sizes were calculated from the
activation of molecular oxygen. This relationship confirms our Au(111) diffraction peaks by using the Scherrer equation:
earlier suggestion that the NPG should be considered more as D = K l/b cosq, in which K = 0.89 is the Scherrer’s constant, l is the
a bifunctional catalyst (comparable to supported Au catalysts) wave length of the X-ray, and b is the FWHM. To determine the
rather than as a truly unsupported Au catalyst.[20] surface concentration of the residual Ag, X-ray photoelectron (XP)

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].

TAP measurements Acknowledgements


[35]
Pulse experiments were carried out in a self built TAP reactor,
which is largely based on the TAP-2 approach of Gleaves et al.[36] In This work was supported by the Baden-Wrttemberg Stiftung
short, piezo-electric pulse valves were used to generate gas pulses within the Network ‘Functional Nanostructures’. L.C. Wang is
of typically  1  1016 molecules per pulse. For all of the measure- grateful for a fellowship from the Alexander-von Humboldt-Foun-
ments presented, these pulses contained 50 % Ar as an internal dation. We gratefully acknowledge T. Diemant for the XPS meas-
standard to enable quantitative evaluation on an absolute scale.
urements, U. Hçrmann for the SEM measurements and S. Blessing
The gas pulses were directed into a quartz tube microreactor. The
for the XRD analyses (all at Ulm University).
catalyst bed was located in its central part and was fixed by two
stainless steel sieves (Haver & Boecker OHG, transmission 25 %). For
all of the measurements, we used a three zone catalyst bed con- Keywords: alloys · gold · microreactors · nanostructures ·
taining 2 mg of the NPG catalyst diluted with 20 mg of SiO2 as the oxidation · silver
central zone and two layers of SiO2 as the outer zones (total mass
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