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C.
Therefore, this method requires high capital cost and high
operating cost. Adsorption is a very useful method in re-
covering expensive solvents and operating in large capac-
ity. But it also requires high capital cost and operating cost.
Catalytic oxidation can be operated at lower temperatures,
typically 300600
C
in air. The calcined catalysts were subsequently reduced in
a H
2
ow with rate of 50 ml/min at room temperature and
at 400
C at 10 min
1
under air ow and the tem-
perature was maintained for 2 h to calcine the catalysts.
Then the catalyst was cooled to room temperature under
He ows. The ow was then switched to H
2
and the tem-
perature was raised to 500
. A
proportional counter and a 0.04
C for 1 h under H
2
to be reduced and
then cooled in H
2
to room temperature. After the reaction
other samples were cooled to room temperature under He
ow. All samples were made airtight.
TEM images of catalysts before and after reaction were
acquired with a JEOL TEM-200CX transmission electron
microscope. Suitable transmission specimens were prepared
H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125131 127
by dispersing the catalyst powders in non-polar solvent
(ethanol) and placing a drop of the suspension onto a carbon
lm supported on a 200 mesh copper grid.
3. Results and discussion
All catalysts were pretreated with hydrogen. Earlier re-
sults indicated that hydrogen treatment may cause Pd en-
richment on surfaces [14].
Fig. 1 shows comparison of light-off curves over different
Pt-Pd catalysts. Pt-Pd bimetal catalysts have better conver-
Fig. 1. Light-off curves for benzene combustion over mPt2Pd and 03PtnPd. (m: 0.3, 1, 0 n: 0.5, 1, 2).
Fig. 2. Light-off curves for benzene combustion over (a) 03PtnPd (b) 1PtnPd (c) 3PtnPd (n: 0, 0.5, 2).
sion values than mono-metal catalysts. Pt-Pd bimetallic cat-
alysts have a good conversion due to the synergetic effect of
Pd metal and Pt metal. 03Pt2Pd catalysts have the most ex-
cellent activity among Pt-Pt bimetal catalysts. As shown in
Fig. 2ac, there is a close relation between Pt/Pd ratio and
the shape of the conversion. mPt-nPd catalyst with relatively
large Pt/Pd ratio gradually becomes similar to the shape of
the conversion on mPt mono-metal catalysts. For example,
the shape of the 3Pt0.5Pd curve in Fig 2c is more similar to
the shape of the 3Pt curve than to that of 3Pt2Pd.
Pd particles on Al
2
O
3
surfaces were covered with Pt in
bimetal catalysts containing excess Pt loading. The activity
128 H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125131
Table 3
Conversion of benzene of pretreated catalysts and catalysts after reaction
at 250
C
First run: H
2
pretreatment (10% H
2
,
90% N
2,
500
C, 2 h) (%)
Second run: recycle
test after reaction (%)
03Pt-r 87.23 86.89
2Pd-r 76.68 74.8
03Pt-2Pd-r 99.5 99.0
of bimetal catalysts with excess Pt loading decreases, though
commonly, the activity of Pt is superior to that of Pd in VOCs
oxidation. This result is consistent with the XPS results.
Table 3 shows the activity of the pretreated samples and
the samples recycled after the reaction. The activities of
03Pt catalysts and 03Pt2Pd catalyst had little change in the
second run compared to the rst run. But the activity of 2Pd
catalysts in the second run is lower than that in the rst run.
This result is said to be related to the oxidation state of Pt
and Pd [15,16].
Fig. 3 shows the time-course of the catalytic activities of
supported 2Pd and 03Pt2Pd catalyst in benzene combustion
at 350
) than other
catalysts after reduction. The binding energy of Pd 3d on all
catalysts is shifted to a higher level after reaction. Pd state
of all catalysts after reactions was shifted more toward PdO.
The binding energy values of all catalysts after reactions
are similar to each other, ranging around 336.55 0.15 eV.
There is no difference among the oxidation states of all
catalysts after reactions.
Fig. 6 shows the relative intensities of the spectra of Pd
3d catalysts with different Pt, Pd loading weights before re-
action. The relative intensity of Pd 3d spectra in catalysts
with increasing Pt contents gradually decreased (2Pd >
03Pt2Pd > 1Pt2Pd > 3Pt2Pd). There is a close correlation
between these results and the activity values of catalysts.
Figs. 7 and 8 display XPS peak deconvolution results
before and after reaction of 03Pt2Pd and 2Pd. As shown in
130 H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125131
Fig. 6. Pd 3d spectra of mPt-nPd catalyst before and after reaction.
Fig. 7. Curve tting of Pd 3d spectra of 2Pd-r catalyst and 03Pt2Pd before and after reaction (a) 03Pt2Pd-r and (b) 03Pt2Pd-a.
Fig. 8. Curve tting of Pd 3d spectra of 2Pd-r catalyst and 03Pt2Pd before and after reaction (a) 2Pd-r and (b) 2Pd-a.
Figs. 6 and 7 and Table 3, results of deconvolution show that
the Pd/Al ratio of Pd 3d peak in 03Pt2Pd had little change
after reactions compared to that of Pd 3d peak in 2Pd. Also
the metal ratio of 03P2Pd-r was kept after reactions unlike
the metal ratio of other catalysts. From these XPS results
and activity results, we suppose that the metal ratio of Pd
and Pd/Al ratio are closely related to activity.
Under excess oxygen, oxidation and reduction are con-
tinually repeated during the reaction. Benzene is oxidized,
and Pd catalyst supported on alumina can easily undergo a
phase transformation between the metallic Pd and the oxi-
dized PdO state during the reaction [22,23]. But the reason-
able addition of Pt maintains Pd metal state and Pd/Al ratio
under low temperature and excess oxygen. It is known that
Pd easily changes to oxidized PdO
x
commonly under the
excess oxygen and low temperature.
Therefore these results presume the addition of suitable
amount of Pt made Pd to take an optimum state for benzene
combustion. On the contrary, the addition of Pt beyond a
certain amount decreases the activity because of the Pd active
site overlapped with Pt.
H.S. Kim et al. / Applied Catalysis A: General 280 (2005) 125131 131
4. Conclusion
In the XRD and TEM results, the high dispersion and
the formation of small particles and the uniform size dis-
tribution in bimetal catalysts are supposed to increase ac-
tivity and stability because the Pt addition has an inuence
on the interaction between the Pd and the support. In XPS
results, Pd/Al ratio of 03tP2Pd-r having the best activity
did not shift after reaction and the metal ratio of 03Pt2Pd-r
was kept after reaction better than those of 1Pt2Pd-r or 2Pd
catalysts.
Pt-Pd bimetallic catalysts are superior to monometallic
Pd, Pt catalysts due to having both Pt active site and Pd
active site in catalytic activity. 03Pt2Pd bimetallic catalyst is
the most active and stable catalyst in benzene combustion.
The most important factor in keeping activity and stability
is the optimum ratio of Pt and Pd. The addition of a suitable
amount of Pt modied Pt-Pd bimetal catalysts to achieve
the optimum state for benzene combustion, but the addition
of Pt beyond a certain amount decreased the activity due
to blockage of active sites (overlapped Pt, Pd active sites).
Therefore an optimum loading weight exists for benzene
combustion.
Acknowledgements
Financial support from the Yonkang Foundation is grate-
fully acknowledged.
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