High-Performance Electrocatalysts for Oxygen Reduction Derived

from Polyaniline, Iron, and Cobalt

Gang Wu, et al.
Science 332, 443 (2011);
DOI: 10.1126/science.1200832

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 REPORTS
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13. A. Maercker, Angew. Chem. Int. Ed. Engl. 26, 972 (1987). 27. Ni(COD)2 and PCy3 were reported to catalyze through the Energy Biosciences Program and
14. P. Dabo, A. Cyr, J. Lessard, L. Brossard, H. Ménard, silane-induced cleavage of polycyclic aromatic ethers T. Rauchfuss for helpful discussions. A provisional patent
Can. J. Chem. 77, 1225 (1999). (methoxynaphthalenes) and alkyl aryl ethers containing has been filed on the methods presented herein.
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Supporting Online Material
16. P. J. Dyson, Dalton Trans. 2964 (2003). as shown through control experiments on the cleavage of www.sciencemag.org/cgi/content/full/332/6028/439/DC1
Materials and Methods
17. E. Wenkert, E. L. Michelotti, C. S. Swindell, J. Am. 4-tert-butylbenzyl methyl ether with hydrogen in the
Chem. Soc. 101, 2246 (1979). presence of AlMe3 (1 equiv.), SIPr·HCl (0.4 equiv.), SOM Text
18. E. Wenkert, E. L. Michelotti, C. S. Swindell, M. Tingoli, and NaOtBu (2.5 equiv.) in m-xylene at 120°C for Figs. S1 to S3
Tables S1 to S6
J. Org. Chem. 49, 4894 (1984). 32 hours (23).
References

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19. J. W. Dankwardt, Angew. Chem. Int. Ed. 43, 2428 29. For example, heterogeneous hydrogenolysis of alkyl
(2004). benzyl ethers proceeds selectively in the presence of 15 November 2010; accepted 11 March 2011
20. B. T. Guan et al., Chem. Commun. (Camb.) 1437 (2008). diaryl ethers over Pd(OH)2/C (35). 10.1126/science.1200437

price of Pt in the volatile and highly monopolized

High-Performance Electrocatalysts precious metal market. The precious metal cat-
alyst is the only fuel cell stack component that
for Oxygen Reduction Derived will not benefit from economies of scale, and an
increase in the demand for fuel cell power sys-
from Polyaniline, Iron, and Cobalt tems is bound to drive up the already high price
of Pt, about $1830 per troy ounce at present
($2280 per troy ounce at its maximum in March
Gang Wu,1 Karren L. More,2 Christina M. Johnston,1 Piotr Zelenay1* 2008) (3). Thus, PEFCs are in need of efficient,
durable, and inexpensive alternatives to Pt and
The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) Pt-based catalysts.
has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of Ideally, Pt should be replaced at both fuel cell
non–precious metal catalysts that approach the performance of platinum-based systems at a electrodes; however, its substitution at the cath-
cost sustainable for high-power fuel cell applications, possibly including automotive power. The ode with a non–precious metal catalyst would
approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature have comparatively greater impact, because the
synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze slow oxygen reduction reaction (ORR) at this
the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported electrode requires much more Pt than the faster
platinum, combining their high activity with remarkable performance stability for non–precious hydrogen oxidation at the anode. As a conse-
metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron quence, the development of non–precious metal
selectivity (hydrogen peroxide yield <1.0%). catalysts with high ORR activity has recently
become a major focus of PEFC research (4–8).
hanks to the high energy yield and low scale market introduction of fuel cell–powered The Pt replacement candidates that have attracted

T environmental impact of hydrogen oxida-

tion, the polymer electrolyte fuel cell (PEFC)
represents one of the most promising energy
vehicles continues to face various challenges, such
as the lack of hydrogen infrastructure and the
technical issues associated with PEFC perform-
the most attention have been synthesized by heat-
ing precursors comprising nitrogen, carbon, and
geologically abundant transition metals, iron and
conversion technologies available today. Of the ance and durability under the operating condi- cobalt (M = Co and/or Fe) in particular (9–14).
many possible applications, ranging from sub-watt tions of an automotive power plant. The high cost Although the nature of the active ORR catalytic
remote sensors to residential power generators in of producing PEFCs represents the most formi- sites in such N-M-C catalysts continues to be at
excess of 100 kW, automotive transportation is dable challenge and has driven much of the ap- the center of an ongoing debate (6, 7, 10, 15),
especially attractive. PEFCs promise major im- plied and fundamental fuel cell research in recent there is no doubt that the ORR performance of
provements over gasoline combustion, including years. N-M-C catalysts strongly depends on the type of
better overall fuel efficiency and reduction in emis- According to the latest cost analysis, the fuel nitrogen and transition-metal precursors used, heat
sions (including CO2). The spectacular progress cell—more precisely, the fuel cell stack—is re- treatment temperature, carbon support morphol-
in fuel cell technology notwithstanding, a large- sponsible for more than 50% of the PEFC pow- ogy, and synthesis conditions.
er system cost (1, 2). Although a state-of-the-art We recently initiated a research effort to develop
1
PEFC stack uses several high-priced components, non–precious metal catalysts that combine high
Materials Physics and Applications Division, Los Alamos National the catalysts are by far the most expensive con- ORR activity with good performance stability, orig-
Laboratory, Los Alamos, NM 87545, USA. 2Materials Science and
Technology Division, Oak Ridge National Laboratory, Oak Ridge, stituent, accounting for more than half of the inally concentrating on materials obtained with-
TN 37831, USA. stack cost. Because catalysts at both the fuel cell out heat treatment. The polypyrrole (PPy)-Co-C
*To whom correspondence should be addressed. E-mail: anode and cathode are based on platinum (Pt) or system prepared this way showed respectable per-
[email protected] platinum alloys, their cost is directly linked to the formance durability for a non–precious metal

www.sciencemag.org SCIENCE VOL 332 22 APRIL 2011 443

REPORTS
catalyst, but its oxygen reduction activity re- in 0.1 M HClO4 to avoid performance loss caused as low as 0.6% at 0.40 V. Unlike other non–
mained relatively low (5). We then shifted toward by bisulfate adsorption, especially at higher elec- precious metal catalysts, which show a peroxide
high-temperature systems synthesized using pre- trode potentials (22). As established in previous yield in excess of 50% at lower loadings (26),
dominantly iron, cobalt, and heteroatom polymer research (23), at sufficiently high electrode over- the H2O2 yield measured with PANI-derived
precursors (polypyrrole and polyaniline) (16, 17). potentials, carbon black alone can act as an oxy- catalysts shows little loading dependence. Even
Such nitrogen-derived non–precious metal ORR gen reduction catalyst (mostly to H2O2 rather at a low loading of 0.1 mg cm−2, the H2O2 yield
catalysts have been under development for sev- than H2O; see Fig. 2A, plot 1). Although the high measured with the PANI-Fe-C catalyst is limited
eral decades, starting with the early work by ORR overpotential on carbon can be lowered by to a range of 0.6 to 3.8%, depending on electrode
Jasinski (18) and by Yeager and co-workers (19). a heat treatment alone (Fig. 2A, plot 2), a more potential.
Their research concentrated in particular on substantial improvement in ORR activity, re- The disparity in the precious and non–
pyrolyzed transition metal–containing macro- flected by a shift in the onset ORR potential from precious metal catalyst loading notwithstanding,
cycles and yielded catalysts that offered good 0.60 to 0.80 V (versus the reversible hydrogen the performance gap between a state-of-the-art
ORR activity but suffered from poor stability in electrode, RHE), is achieved after the addition of Pt/C (E-TEK) and PANI-Fe-C, expressed as a
an acidic environment (20). The expensive macro- PANI (Fig. 2A, plot 3). Pyridinic, pyrrolic, and half-wave potential difference (DE½) in rotating
cycles were later replaced in numerous studies quaternary nitrogen centers are present in the disk electrode (RDE) testing, has been substan-
by various combinations of nitrogen-containing heat-treated PANI-C sample (24). Nitrogen can tially reduced in this work to 43 mV relative to Pt/C
compounds, transition-metal inorganic salts, and be viewed in this case as an n-type carbon dopant at a “standard” loading of 20 mgPt cm−2 (Fig. 2A)
carbons, which ultimately led to considerable im- that results in the formation of disordered car- and 59 mV relative to Pt/C at a “high” loading of
provements in ORR activity but relatively little bon nanostructures and/or donates electrons to 60 mgPt cm−2.

Downloaded from www.sciencemag.org on April 25, 2011

progress in stability. Polyaniline (PANI), which the carbon (24), thus facilitating the ORR (25). Whereas cyclic voltammograms (CVs) of
represents a favorable combination of aromatic Iron or cobalt incorporation leads to a radical PANI-C and PANI-Co-C in N2-saturated H2SO4
rings connected via nitrogen-containing groups, enhancement in the ORR activity and four- solution are virtually featureless, the CVof PANI-Fe-C
was selected for this study as a promising template electron selectivity of the catalysts (Fig. 2A, plots reveals a pair of well-developed redox peaks at
compound for nitrogen and carbon. Because of the 4 and 7). The ORR onset potential for the more ~0.64 V (fig. S1). The full width at half maxi-
similarity between the structures of PANI and gra- active of the two PANI-FeCo-C catalysts and mum (FWHM) of these peaks is ~100 mV, which
phite, the heat treatment of PANI could facilitate for the PANI-Fe-C catalyst is ~0.93 V (bottom is very close to the theoretical value of 96 mV
the incorporation of nitrogen-containing active part of Fig. 2A, plots 6 and 7, respectively). A expected for a reversible one-electron process in-
sites into the partially graphitized carbon matrix. rotating ring-disk electrode (RRDE) study ad- volving surface species (27). There are two sur-
Furthermore, the use of such a polymer as a ni- ditionally reveals very high selectivity of the PANI- face processes that can possibly give rise to the
trogen precursor promised a more uniform dis- derived catalysts for the four-electron reduction observed redox behavior in this case: (i) one-
tribution of nitrogen sites on the surface and an of oxygen. The H2O2 yield with PANI-Fe-C electron reduction/oxidation of the surface quinone/
increase in the active-site density. In our effort, remains below 1% at all potentials, dropping to hydroquinone groups (28), and (ii) Fe3+/Fe2+
although several catalysts have shown promising
oxygen reduction activity, only PANI-derived for-
mulations appear to combine high ORR activity
with unique performance durability for heat-treated
non–precious metal catalysts. These catalysts are
the subject of this report.
A schematic diagram describing the catalyst
synthesis is shown in Fig. 1. In the approach
used, a short-chain aniline oligomer was first
mixed with high–surface area carbon material,
pristine Ketjenblack EC-300J or modified Ketjen-
black in the case of PANI-FeCo-C(2) (21), and
transition metal precursors [cobalt(II) nitrate and/
or iron(III) chloride], followed by the addition of
(NH4)2S2O8 (ammonium persulfate, APS) as an
oxidant to fully polymerize the aniline. After
polymerization, water was evaporated from the
suspension and the remaining solid phase was
subjected to heat treatments in the range 400° to
1000°C under a N2 atmosphere. The heat-treated
product was then preleached in 0.5 M H2SO4 at
80° to 90°C for 8 hours to remove any unstable
and ORR-nonreactive phases. The preleached
catalyst then underwent a second heat treatment
under N2 as the final step of the synthesis (21).
The ORR activity and four-electron selectiv-
ity of various PANI-M-C catalysts and several
control materials (as-received and heat-treated
carbon, heat-treated metal-free PANI-C, and a
20 weight percent Pt/C reference catalyst) are Fig. 1. Schematic diagram of the synthesis of PANI-M-C catalysts. (A) Mixing of high–surface area carbon
shown in Fig. 2A. All experiments involving non– with aniline oligomers and transition-metal precursor (M: Fe and/or Co). (B) Oxidative polymerization of
precious metal catalysts were carried out in 0.5 M aniline by addition of APS. (C) First heat treatment in N2 atmosphere. (D) Acid leaching. The second heat
H2SO4. The Pt/C reference catalyst was tested treatment after acid leach is not shown.

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 REPORTS
reduction/oxidation. In support of the latter reac- cative of coordination to a lighter element (either lysts with the heat treatment temperature. Fourier
tion, an in situ electrochemical x-ray absorption N or O) at a much shorter distance than nearest transform infrared (FTIR) spectra of PANI-Fe-C
study of the PANI-Fe-C system shows a cor- neighbors in metallic Fe (XAFS peak at ~2.2 Å) (fig. S3) show that between 400° and 600°C
relation between the change in the oxidation state or in FeN4-type structures in Fe macrocycles the benzene-type (1100 cm−1) and quinone-type
of Fe species in the catalysts and the potential of (~1.63 Å) (30). (1420 cm−1) structures (32) on the main PANI
the reversible CV feature in the PANI-Fe-C cat- In catalyst synthesis chemistry, the heat chain break into smaller fragments, such as C=N
alyst voltammetry (17). treatment temperature is a major factor in induc- (1300 cm−1), which may be precursor states for
Additional kinetic data (fig. S2 and table S1) ing catalytic activity of PANI-derived catalysts ORR-active sites. The latter finding corresponds
reveal differences in the Tafel slope of oxygen and assuring performance stability. We used an with scanning electron microscopy (SEM) results
reduction on the different catalysts studied in this RDE to study the ORR activity of a PANI-Fe-C (fig. S4) indicating that in this range of heat treat-
work. A Tafel slope of 67 mV decade−1 was mea- catalyst as a function of the heat treatment tem- ment temperatures, PANI starts to lose its char-
sured for PANI-Co-C—a much lower value perature in the range 400° to 1000°C. RDE studies acteristic nanofibrous structure (fibers ~40 nm
than the Tafel slope of 87 mV decade−1 obtained were conducted at room temperature and in 0.5 in diameter and ~200 nm in length) and grad-
for PANI-Fe-C. The rate-determining step of the M H2SO4 electrolyte (Fig. 2B). The performance ually converts into more spherical particles. The
ORR for the latter catalyst is likely to simulta- of the catalyst synthesized by heat treatment at carbon structure becomes more graphitic dur-
neously involve the migration of reaction inter- 400°C is very similar to that of Ketjenblack itself ing the heat treatment at 900°C (HRTEM inset
mediates and charge transfer. The exchange (bottom part of Fig. 2A, plot 1). The activity, as in fig. S4) (see below). After the treatment at an
current density (i0) is nearly two orders of mag- measured by the ORR onset and half-wave po- even higher temperature of 1000°C, the particle
nitude higher for the PANI-Fe-C catalyst (4 × 10−8 tentials (E½) in the RDE polarization plots, in- morphology becomes highly nonuniform, a change

Downloaded from www.sciencemag.org on April 25, 2011

A cm−2) than for PANI-Co-C (5 × 10−10 A cm−2). creases upon raising the heat treatment temperature accompanied by a substantial surface area loss, as
Together with the differences in the onset potential up to 900°C and then drops for catalysts synthe- determined using Brunauer-Emmet-Teller (BET)
of oxygen reduction (21), the Tafel slope (mass sized at even higher temperatures. The H2O2 yield technique.
transport–corrected), and four-electron selectivity measured for the best-performing PANI-Fe-C The fuel cell polarization and stability plots
(Fig. 2A) already described, the disparity of two catalyst, heat treated at 900°C, is below 1% over for PANI-derived catalysts are shown in Fig. 3. In
orders of magnitude in the i0 value for the two the potential range from 0.1 to 0.8 V versus RHE, good agreement with electrochemical measure-
catalysts implies that the ORR-active sites and signaling virtually complete reduction of O2 to ments, the addition of transition metals leads to a
reaction mechanisms are likely different in both H2O in a four-electron process. This avoidance of considerable activity enhancement of the cata-
cases. Ex situ x-ray absorption analysis provides the much less efficient, and therefore undesirable, lysts relative to the metal-free PANI-C (Fig. 3A).
evidence for a different chemical environment in two-electron reaction to peroxide matches, and Also in agreement with the RDE data in Fig. 2A,
each case. Cobalt coordination in the PANI-Co-C possibly exceeds, the four-electron selectivity of PANI-Fe-C exhibits higher ORR activity than
catalyst appears to closely resemble that in Co9S8, Pt-based catalysts (3 to 4% H2O2 yield at 0.4 Von PANI-Co-C. The best-performing catalyst in fuel
with the dominant x-ray absorption fine structure 14 mgPt cm−2 Pt/C) (31). cell testing, with an excellent combination of high
(XAFS) peak between 2 to 3 Å consistent with a We next conducted extensive physical char- ORR activity and long-term performance dura-
known Co-Co shell (29). XAFS of the PANI-Fe-C acterization to obtain a structural explanation for bility, is the more active of the two FeCo mixed-
catalyst shows a peak at ~1.50 Å, which is indi- the correlation of the ORR activity of the cata- metal materials, PANI-FeCo-C(2). This catalyst

Fig. 2. (A) Steady-state ORR

polarization plots (bottom)
and H2O2 yield plots (top)
measured with different PANI-
derived catalysts and reference
materials: 1, as-received car-
bon black (Ketjenblack EC-
300J); 2, heat-treated carbon
black; 3, heat-treated PANI-C;
4,PANI-Co-C;5,PANI-FeCo-C(1);
6: PANI-FeCo-C(2); 7, PANI-
Fe-C; 8, E-TEK Pt/C (20 mgPt
cm−2).Electrolyte: O2-saturated
0.5 M H2SO4 [0.1 M HClO4 in
experiment involving Pt cat-
alysts (dashed line)]; temper-
ature, 25°C. RRDE experiments
were carried out at a constant
ring potential of 1.2 V versus
RHE. RDE/RRDE rotating speed,
900 rpm; non–precious metal
catalyst loading, 0.6 mg cm−2.
(B) Steady-state ORR polariza-
tion plots (bottom) and H2O2
yield plots (top) measured with
a PANI-Fe-C catalyst in 0.5 M
H2SO4 electrolyte as a function
of the heat treatment temper-
ature: 1, 400°C; 2, 600°C; 3, 850°C; 4, 900°C; 5, 950°C; 6, 1000°C.

www.sciencemag.org SCIENCE VOL 332 22 APRIL 2011 445

REPORTS
also shows the highest RDE activity, matched at 0.38 V. Unlike PANI-Fe-C, the mixed-metal acidic environment of the fuel cell cathode, thus
only by PANI-Fe-C (see low current-density range catalysts maintain their high ORR activity when reflecting better stability of the PANI-FeCo-C
in Fig. 2A, plots 6 and 7), as well as the highest combined with Nafion ionomer in a fuel cell– catalyst (see below). The open-cell voltage (OCV)
maximum power density: 0.55 W cm−2, reached type electrode under operation in the highly of a hydrogen fuel cell operated with Fe-containing

Downloaded from www.sciencemag.org on April 25, 2011

Fig. 3. Fuel cell and performance durability testing. (A) H2-O2 fuel cell polarization PANI-FeCo-C(1) catalyst at a constant fuel cell voltage of 0.40 V (2.8 bar H2/2.8 bar
plots recorded with various PANI-derived cathode catalysts at a loading of ~4 mg cm−2: air; 0.25 mgPt cm−2 anode; cell temperature 80°C). (C) PANI-Fe-C catalyst RDE
1, PANI-C; 2, PANI-Co-C; 3, PANI-FeCo-C(1); 4, PANI-FeCo-C(2) (SDs from three performance at various potentials after potential cycling in nitrogen between 0.6
independent measurements marked for all data points); 5, PANI-Fe-C. Performance and 1.0 V in 0.5 M H2SO4 (catalyst loading, 0.6 mg cm−2). (D) PANI-Fe-C catalyst
of an H2-air fuel cell with a Pt cathode (0.2 mgPt cm−2) is shown for comparison H2-O2 fuel cell performance at various voltages after voltage cycling in nitrogen
(dashed line). All tests used a Pt/C catalyst at a loading of 0.25 mgPt cm−2 at the between 0.6 and 1.0 V (cathode catalyst loading, 2.0 mg cm−2, Pt/C anode
anode; anode and cathode gas pressure, 2.8 bar. (B) Long-term stability test of a catalyst loading, 0.25 mgPt cm−2; anode and cathode gas pressure, 1.0 bar).

Fig. 4. Micrographs of a PANI-FeCo-C(1) catalyst. (A) HRTEM image of a typical STEM, and SEM images of the same localized region in an area exhibiting a
non–precious metal catalyst nanostructure involving carbon nanofibers and metal- graphene sheet–like structure, where the green arrows designate the layered
aggregates incorporated in graphitic nanoshells. (B) HRTEM image of hollow graphene sheet in each image and the red arrows designate the same FeCo-
nanoshells. (C) HRTEM image of onion-like nanoshells. (D to F) HRTEM, HAADF- containing nanoparticle (technique used is noted in each micrograph).

446 22 APRIL 2011 VOL 332 SCIENCE www.sciencemag.org

 REPORTS
PANI-derived catalysts is ~0.90 V with an air- well-defined graphitized carbon shell surround- 6. M. Lefèvre, E. Proietti, F. Jaouen, J. P. Dodelet,
operated cathode and ~0.95 V with a cathode op- ing metal-rich particles was previously observed Science 324, 71 (2009).
7. C. M. Johnston, P. Piela, P. Zelenay, in Handbook of Fuel
erated on pure oxygen. The OCV value remains with iron(III) tetramethoxyphenyl porphyrin Cells: Fundamentals, Technology, and Applications,
unchanged for more than 100 hours in the H2-air chloride (FeTMPP-Cl) when the heat treat- W. Vielstich, H. A. Gasteiger, H. Yokokawa, Eds.
fuel cell (17). ment temperature was raised to 1000°C (33). (Wiley, Chichester, UK, 2009), vol. 5, pp. 48–70.
A 700-hour fuel-cell performance test at a con- In the latter work, the graphite shell formation 8. F. Jaouen et al., Energy Environ. Sci. 4, 114 (2011).
9. S. Maldonado, K. J. Stevenson, J. Phys. Chem. B 108,
stant cell voltage of 0.4 V reveals very promising was correlated to an increase in the catalyst 11375 (2004).
performance stability of the PANI-FeCo-C(1) open-circuit potential in oxygen-saturated solu- 10. P. H. Matter, L. Zhang, U. S. Ozkan, J. Catal. 239,
catalyst at the fuel cell cathode. The cell cur- tion. Carbon nanosheets grown over the metal 83 (2006).
rent density in a lifetime test (Fig. 3B) remains particles are also observed in Fig. 4, A and B. 11. R. Kothandaraman, V. Nallathambi, K. Artyushkova,
nearly constant at ~0.340 A cm−2. The current In some cases, the metallic cobalt and/or iron S. C. Barton, Appl. Catal. B 92, 209 (2009).
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value of 0.347 A cm−2 in the first 24 hours to particles can be removed by acid leaching, leav- 13. F. Jaouen et al., ACS Appl. Mater. Interfaces 1,
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R. Mukundan, H. Chung, and S. Conradson for stimulating
The morphology of the highly ORR-active intrinsic activity and durability between non–
discussions. Supported by the Energy Efficiency and
and durable PANI-FeCo-C(1) catalyst before precious metal catalysts and platinum in PEFCs Renewable Energy Office of the U.S. Department of
and after the heat treatment at 900°C (followed will require determination of the active oxygen Energy (DOE) through the Fuel Cell Technologies Program,
by acid leaching) is depicted by the SEM im- reduction site and a better understanding of the and by Los Alamos National Laboratory through the
ages in fig. S6. In this catalyst, as in PANI-Fe-C, reaction mechanism. Laboratory-Directed Research and Development Program.
Microscopy research was supported by the Oak Ridge
the PANI nanofibers are replaced by a highly National Laboratory’s SHaRE User Facility, sponsored by the
graphitized carbon phase during heat treatment. References and Notes DOE Office of Basic Energy Sciences. The authors have filed
High-resolution transmission electron micros- 1. B. James, J. Kalinoski, in DOE-EERE Fuel Cell a patent through Los Alamos National Laboratory on the
copy (HRTEM) and high-angle annular dark- Technologies Program—2009 DOE Hydrogen Program catalysts described herein.
field scanning TEM (HAADF-STEM) images Review (www.hydrogen.energy.gov/pdfs/review09/
fc_30_james.pdf ). Supporting Online Material
of the PANI-FeCo-C(1) catalyst heat-treated at 2. J. Sinha, S. Lasher, Y. Yang, in DOE-EERE Fuel Cell www.sciencemag.org/cgi/content/full/332/6028/443/DC1
900°C are shown in Fig. 4 and attest to the pres- Technologies Program—2009 DOE Hydrogen Program Materials and Methods
ence of diverse carbon nanostructures, also high- Review (www.hydrogen.energy.gov/pdfs/review09/ Table S1
lighted in HRTEM images in figs. S7 and S8. fc_31_sinha.pdf ). Figs. S1 to S8
3. Johnson Matthey (www.platinum.matthey.com/ References
Metal-containing particles are to a large extent pgm-prices/price-charts).
encapsulated in well-defined onion-like graphit- 4. R. Borup et al., Chem. Rev. 107, 3904 (2007). 23 November 2010; accepted 24 March 2011
ic carbon nanoshells (Fig. 4, A and C). Such a 5. R. Bashyam, P. Zelenay, Nature 443, 63 (2006). 10.1126/science.1200832

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