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org/cgi/content/full/323/5917/1037/DC1
Supported catalysts were prepared by incipient wetness impregnation of support materials: carbon
(Aldrich G60)*, silica (Grace, Johnson Matthey) -Al2O3 (Condea SCF-140) and TiO2 (Degussa
P25) with aqueous solutions of PdCl2 (Johnson Matthey) and/or HAuCl4.3H2O (Johnson Matthey)
and were calcined (400 oC, 3 h). Supports (10 g) were pre-treated either with water (100 ml) or with
dilute HNO3 in water (2 %, 10 %, 30 % and 60 % volume fraction, 100 ml) for 3 h at ambient
Catalyst testing for the direct synthesis of H2O2 was performed as previously described13. H2
conversion was calculated by gas analysis before and after reaction. H2O2 selectivity was
calculated by relating moles of H2O2 formed to moles of H2 consumed and can be determined to an
Samples for TEM and STEM analysis were prepared by dispersing the catalyst powder in
high purity ethanol, then allowing a drop of the suspension to evaporate on a holey carbon film
supported by a 300 mesh copper TEM grid. Particle size distributions were determined from the
analysis of bright field images taken in a JEOL 2000FX TEM operating at 200kV. Chemical
microanalysis was performed in a FEI Titan 80-300 operating in STEM mode at 300 kV. This
instrument was fitted with a CEOS double-hexapole spherical aberration-corrector and an EDAX r-
TEM Si(Li) detector system for energy dispersive X-ray (XEDS) analysis. Drift-corrected XEDS
spectrum images were acquired from 0 keV to 40 keV with a dispersion of 10 eV/channel. The
pixel size of the images was 1nm x 1nm and a probe dwell-time of 250 ms per pixel was employed.
Data extraction and processing were performed using NIST Lispix v102
(http://www.nist.gov/lispix/).
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Results
ICP analysis
Inductively coupled plasma analysis was carried out to determine the nature of the trace impurities
in the bulk of untreated and the pre-treated carbon (Aldrich G60) and also the analysis of the 2%
HNO3 solution used for the pre-treatment. The results are shown in Figure S1. It is clear that the
pre-treatment of the carbon support does not effect the concentration of most of the trace impurities;
Na and K concentrations are, however, altered with Na being decreased and K being increased.
However, we have shown (main text Table 1) that pre-treatment with NaNO3 and KNO3 had no
effect on the catalytic performance of the Au-Pd catalysts. Hence, we consider that the effect
observed on the catalysis by acid pre-treatment is not due to alterations in the trace impurities
XPS analyses
The XPS survey spectrum (Fig S2) demonstrates that acid treatment does not affect the
overall chemical composition of the carbon support surface. However, significant differences are
observed between the fresh and acid pre-treated supports after Au-Pd impregnation followed by
calcination at 400 oC. The surface Pd:Au ratio (Figs S3(a), S3(b)) for calcined Au-Pd/carbon with
the untreated support (Pd:Au = 3.5:1 by weight) is significantly higher than that of the acid pre-
600
500
Assay / ppm by weight
400
300
200
100
0
Fe
Zr
Ti
K
g
l
i
P
W
Sr
V
Sb
g
a
n
Zn
B
Bi
r
u
Ba
Sn
a
Si
A
N
M
A
N
M
C
Figure S1: ICP analysis of G-60 carbon and 2% HNO3 solution. Key: solid black: untreated;
Figure S2: Survey spectra for the untreated and acid pre-treated carbon support.
5
Figure S3(a): Au(4f) spectra for the untreated and acid pre-treated carbon support.
Figure S3(b): Pd(3d) spectra for the untreated and acid pre-treated carbon support.
6
i.)
v.)
Figure S4: STEM XEDS and particle size distributions for acid pre-treated and non-treated
catalysts. A - Representative STEM-XEDS data sets for the unwashed (i-iv) and acid-washed (v-
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viii) Au-Pd/C catalysts. Shown are the STEM high-angle annular dark-field images (i,v) with
accompanying Au-M (ii,vi) and Pd-L (iii,vii) XEDS maps. Color overlay maps wherein green =
Figure S5: HAADF micrograph of the 2.5%Au 2.5% Pd/C acid pre-treated catalyst after aging for
98 h. Note the existence of intermediate and small metal particles even after use.
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Table S1: Hydrogen peroxide yield after hydrogenation, decomposition and synthesis in the
1
2.5 %Au-2.5 % Pd/carbon catalysts (Aldrich G60) calcined in air 400 oC, 3h.
2
Standard H2O2 synthesis conditions with an initial H2O2 mass fraction of 4.3 %.
3
Standard H2O2 hydrogenation conditions with an initial H2O2 mass fraction of 4.3 % .
4
Decomposition reactions were carried out in the presence of 2.5 % O2/CO2 (1.1MPa) in the
the National Institute of Standards and Technology, nor does it imply that the materials or
equipment identified are necessarily the best available for the purpose.