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INTRODUCTION
DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
Forum Article
EXPERIMENTAL SECTION
DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
Forum Article
DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
Forum Article
Figure 3. XPS of (a) Co 2p core level spectra of CZ composite, (b) Zr 3d core level spectra of CZ composite, (c) Pd 3d core level spectra of PdCZ, and
(d) Pt 4f core level spectra of PtCZ, (e) Pd 3d core level spectra of PdCZ after 50 h, (f) Pt 4f core level spectra of PtCZ after 50 h.
Figure 4. Variation in H2 conversion with temperature (a) at various initial H2 concentrations in the presence of PdCZ catalyst (with 10 vol % O2,
GHSV = 47750 h1, catalyst loading = 25 mg), (b) for CZ, PtCZ, and PtCZ catalysts (with H2:O2:N2 = 5:10:85 vol %, GHSV = 47750 h1, catalyst
loading = 25 mg).
DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
Forum Article
Table 1. Activation Energies, Catalyst Loading, and Dopant Loading of Various Catalysts for Catalytic Hydrogen Combustion
activation energy,(kJ mol1)
catalyst
temperature range
dopant loading
Pd/Al2O3
Pt/Al2O3
(Pd65Pt35)2.79%/Al2O3
70140 C
4090 C
4090 C
36
41
40
2000
2000
2000
(Pd20Pt80)2.79%/Al2O3
70110 C
44
2000
Cu/SnO2
Cu/CeO2
Cu/Al2O3
Cu/ZrO2
Pd/Monolith supports
0.5 (wt %) Pd/Al2O3
Pt/SiC washcoat
Co3O4 ZrO2
Pt/Co3O4 ZrO2
Pd/Co3O4 ZrO2
220300 C
220300 C
220300 C
240340 C
27.6
31.5
38.8
56
26
73.8
34
34.3 2.3
39.3 2.0
13.4 1.2
0.92 wt %
1.78 wt %
Pt = 1.38 wt %
Pd = 1.41 wt %
Pt = 0.20 wt %
Pd = 1.41 wt %
5 at %
5 at %
5 at %
5 at %
3585 C
2550 C
180210 C
3060 C
3060 C
200
200
200
200
30000
400
50
25
25
0.5 wt %
0.27 wt %
0
2 at %
2 at %
ref
4
4
4
4
34
34
34
34
44
45
13
present study
present study
present study
Figure 5. Conversion of H2 with catalyst loading (W) for (a) CZ, (b) PdCZ, and (c) PtCZ catalysts (with 5 vol % of H2); (d) Arrhenius plot for PdCZ,
PtCZ, and CZ catalysts.
FH2
catalyst loading and FH2 represents the molar ow rate of the H2.
Figure 5 shows the linear variation of H2 conversion with
W
FH2
for
CZ, PtCZ and PdCZ catalysts. The reaction rates were calculated
by, rH2 =
X H2
FH2
DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
Forum Article
Figure 6. (a) H2TPR proles for CZ, PdCZ, and PtCZ catalysts;
(b) H2TPD proles for PdCZ and PtCZ catalysts.
DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
Forum Article
Figure 7. In situ FTIR spectra for (a) CZ; (b) PtCZ; (c) PdCZ catalysts; (d) CZ, PdCZ, and PtCZ catalysts at 50 C.
catalyst
Pd2+
Pd0
PdO
PdCZ
PdCZ-S
88.3
89.8
6.4
0
%
5.3
10.2
catalyst
Pt4+
Pt2+
Pt0
PtO2
PtCZ
PtCZ-S
12.6
58.8
27.3
23.5
52.3
17.7
7.8
0
DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
Forum Article
was not detected after stability study and PdO content increased
to 10.2% from 5.3%. This indicates PtCZ and PdCZ catalysts
are highly stable and more oxidation of noble metal ions was
observed because of maintaining oxygen rich conditions than the
actual requirement according to its stoichiometry.
CONCLUSIONS
Pt- and Pd-substituted CZ catalysts are highly active for
hydrogen combustion. Because of its special features of hydrogen
and oxygen activation (analyzed from H2TPD and H2TPR
studies), 100% conversions were obtained at 100 C and sudden
light-os were observed. In this study, we found that the lattice
oxygen release is insignicant for Pt/Pd substituted CZ but is
crucial with CZ composites. The activation energies of PdCZ is
lowest compared with the other catalysts because eof the
predominant steps of O2 and H2 activation on the catalyst
surface. The noble metal ions were oxidized after 50 h stability
study. From XPS characterization the compositions of Pt4+
increased to 52.3% from 17.7% and no metallic Pd was observed
after the stability study that indicates the enhancement of
availability of oxygen vacancies. This further suggests that both
PtCZ and PdCZ catalysts are stable and durable catalysts for
hydrogen combustion. These studies gave an outlook of such
catalysts for safety applications in nuclear power plants as well as
to remove an excess amount of hydrogen at the outlet of fuel
cells.
AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENTS
The authors are grateful to the Centre for Nanoscience and
Engineering (CeNSE), IISc, for the XRD and XPD facilities and
Department of Advanced Facilities for Microscopic and
Macroscopic analysis (AFMM), IISc, for providing the TEM
facility. G.M. thanks the Department of Science and Technology
(DST), India, for the J.C. Bose fellowship.
REFERENCES
DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX
Forum Article
DOI: 10.1021/acsami.6b08019
ACS Appl. Mater. Interfaces XXXX, XXX, XXXXXX