SCIENCE & TECHNOLOGY
FUEL FROM THE SUN
Cobalt water-oxidation CATALYSTS benefit from federal
initiatives to harness solar power to make fuel
STEPHEN K. RITTER, C&EN WASHINGTON
WATER + SUNLIGHT = FUEL. This equa-
tion embodies the use of solar energy to rip
apart water molecules to produce hydro-
gen, which can be used as an energy-rich
fuel for vehicles and to produce electricity.
If perfected and made affordable, the tech-
nology could supply a substantial portion of
future global energy demand, which is an-
ticipated to double between now and 2050.
Key to solar water splitting is developing
inexpensive catalysts to capture light ef-
ficiently and speed the process while mini-
mizing the amount of electricity needed to
drive the electrochemistry. Most catalysts
so far have less than stellar efficiencies, rely
on expensive and rare metals, or tend to
be easily deactivated under harsh working
conditions.
Two U.S. research groups have recently
reported breakthrough developments that
could signal a new wave of progress in pro-
ducing H2 via solar water splitting. Daniel
G. Nocera and coworkers at Massa-
MIT/NSF
chusetts Institute of Technology have
made a heterogeneous cobalt phos-
phate water-oxidation catalyst with
improved stability. And Craig L. Hill
of Emory University and coworkers
have created a related homogeneous
cobalt catalyst supported by bulky
polytungstate ligands that displays
improved catalytic activity.
Both catalysts are made from
Earth-abundant elements, avoid
organic ligands that are prone to
oxidation during electrolysis, have a
built-in mechanism for self-repair to
© 200 8 SCI EN CE
improve lifetime, and operate at neu-
tral pH with modest electricity input.
But that’s only part of the story.
The catalysts and the researchers de-
veloping them are beneficiaries of a
sudden abundance of federal funding.
For most of the past 30 years,
funding for solar-fuel research was
flat, according to Mark T. Spitler,
manager of the Solar Photochem-
istry program in the Department of
Energy’s Office of Basic Energy Sci-
ences. But since 2005, DOE has been
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flush with money for renewable energy
research and is using it to create new meth-
ods of funding designed to accelerate the
transition of basic research to commercial
applications, Spitler says.
For example, DOE’s Advanced Research
Projects Agency-Energy (ARPA-E) program
has provided hundreds of millions of dol-
lars in three rounds of funding to promising
start-ups and research labs to help them
move high-risk, high-payoff technologies
toward fruition (C&EN, March 22, page 38).
“ARPA-E is a tremendous success story,”
says chemical engineer Amir Nashat, chief
executive officer of Sun Catalytix, in Cam-
bridge, Mass. The company, which Nocera
started last year to develop inexpensive
solar-powered water-splitting systems to
make H2, has garnered more than $4 mil-
lion in ARPA-E funds. “ARPA-E is having
an incredible impact on Sun Catalytix
and other small companies, enabling us
26 J U LY 5, 20 10
to follow our dreams to turn science into
technology and eventually into commercial
products,” Nashat says.
Another new DOE initiative is a set of
three Energy Innovation Hub grants worth
$122 million each for multidisciplinary
teams of dozens of principal investigators
to speed up integrating the various pieces of
promising technologies, Spitler notes. One
of the hubs is aimed at “creating the science
and technology for a solar fuels industry
that currently doesn’t exist,” Spitler says.
Nocera is part of a team based at the Na-
tional Renewable Energy Laboratory that
is a finalist for the solar fuels hub grant,
which will be awarded later this summer.
Hill was part of a team based at Oak Ridge
National Laboratory, but that team didn’t
make the final cut.
Hill says the funding would have been
nice, but he is able to pursue his work with
other DOE funding and Department of
Defense grants. In addition, the National
Science Foundation is funding research on
solar fuels, he notes.
“So much is happening right now in so-
lar fuels and photochemistry, with grants,
meetings, and scientific conferences, it’s
hard to keep up,” Hill says.
COMMERCIAL TECHNOLOGY to derive H2
from water by electrolysis has been available
for nearly a century. Because elec-
trolysis remains expensive, industrial
H2 production continues to be primar-
ily by steam reforming of petroleum
and by coal gasification, both of which
are based on limited fossil resources,
comments Matthias Beller of Leibniz
Institute for Catalysis at Germany’s
University of Rostock, who studies
iron-based H2-generating catalysts.
“Clearly, on a mid- to long-term
basis, there is an essential demand
for alternative technologies to gener-
ate H2 in a more
sustainable
EFFERVESCENT manner if it is
A snapshot of an to be used as a
electrochemical
cell set up in transportation
Nocera’s MIT fuel and for pro-
lab in which ducing electric-
the amorphous ity,” Beller says.
cobalt phosphate
thin-film catalyst “Photocatalytic
(shown in water splitting
micrograph, offers the most
bottom) is straightforward
facilitating water
oxidation to
production of
generate oxygen H2 from H2O.
bubbles. In this respect,
the recent work from the Nocera and Hill
groups is highly interesting.” “Chemists need to start moving on from
Water splitting is a two-stage process.
In an electrolysis cell, water is oxidized at
just focusing on making a water-splitting
the positive electrode, or anode, to form catalyst to making integrated systems.”
O2, along with four hydrogen ions and four
electrons. The hydrogen ions migrate to
the negative electrode, or cathode, where at neutral pH during electrodeposition is similar to the calcium manganese oxide
two H+ ions are reduced by two electrons (C&EN, Aug. 4, 2008, page 7). cluster in the oxygen-evolving complex of
arriving through an external circuit to form When a potential is applied, Co2+ photosystem II, the enzyme nature uses in
H2. Of the two electrode processes, both of oxidizes to Co3+, which precipitates with photosynthesis, Nocera points out.
which require a catalyst to be efficient, the phosphate as an amorphous thin film on But the key feature of Nocera’s catalyst
water-oxidation reaction is more complex an indium tin oxide electrode or fluorine is its ability to repair itself. Catalysts that
and thermodynamically demanding. tin oxide electrode, Nocera explains. The mediate multielectron transformations op-
In fuel cells, which also require catalysts, phosphate serves as a ligand to cobalt oxide erate under harsh conditions, Nocera says.
the opposite reactions take place to release and as an H+ acceptor that shuttles the ions In particular, oxygen-evolving catalysts
the energy stored in the H–H bonds: H2 and from the anode to the cathode, he says. with complex organic ligand systems tend
O2 are fed into a fuel cell, releasing electrons Because the catalyst is an amorphous sol- to easily oxidize, he notes. “Molecular cata-
to make electricity and producing water. id, its exact structure is unknown. Nocera’s lysts with organic ligands appear to break
Electricity to power water splitting can group has used various techniques, includ- down to metal oxides under the harsh con-
come straight from a wall outlet, indirectly ing X-ray absorption, electron paramagnetic ditions,” Nocera adds, “which is why we
from sunlight via a photovoltaic solar cell, resonance, isotope labeling, and computer went to an all-inorganic simple system that
or directly from sunlight at the anode by in- simulations to gain a better understanding stands up over time.”
terfacing the water-oxidation catalyst with of the catalyst and improve its performance. Cobalt phosphate at the catalyst surface
a semiconductor—a photocatalyst. The researchers believe that the active is continuously refreshing itself, Nocera
“Developing efficient and low-cost catalyst is a cobalt oxide cubane cluster explains. His group has shown that Co2+
catalysts and electrode materials for wa- with bridging oxo groups. This structure ions readily exchange phosphate ligands
ter splitting to produce H2 is demanding
technology,” notes Can Li of China’s Da-
lian Institute of Chemical Physics, whose
group works on inorganic semiconducting
photocatalysts for water splitting (C&EN,
Aug. 10, 2009, page 7). “Although H2 pro-
duced in the reduction reaction is the fuel
we need, the key to achieve high-efficiency
water splitting is to solve the water oxida-
tion problem, because it is a kinetically
slower reaction. The cobalt-based oxygen-
evolving catalysts developed by Nocera
and Hill are breakthroughs on the way to
solving this key problem of water oxidation
for efficient overall water splitting.”
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a dilute phosphate-buffered Co2+ solution

WWW.CEN-ONLINE.ORG 27 J U LY 5, 20 10
 during the catalytic cycle and that the Co3+
Q IUSHI Y IN
and Co4+ species present are substitution-
ally inert. Any Co2+ ions released from the
electrode surface and oxidized to Co3+
during water splitting are redeposited with
phosphate on the electrode surface.
IN MARCH, Emory’s Hill and coworkers
reported their cobalt oxygen-evolving
catalyst containing the bulky polytungstate
ligands [Co4(H2O)2(PW9O34)2]10– (C&EN,
March 15, page 48). The catalyst self-as-
sembles in boiling water from Co2+, phos-
phate, and tungstate salts. Its Co4O4 core
is protected from oxidation by a pair of the
polyoxometalate ligands.
The cobalt polytungstate is a homoge-
neous catalyst, so Hill’s team was able to
study its X-ray crystal structure. Because
the catalyst is molecular, it is easier to op-
timize by interchanging ligand units and
interfacing with photosensitizers. And like
Nocera’s catalyst, the self-assembly and
exchangeable ligands enable the catalyst to
constantly repair itself, Hill says.
The key feature of Hill’s catalyst is its
high activity. The team showed that in a
phosphate-buffered pH 8 solution with
ruthenium bipyridine as a chemical oxi-
dant, the catalyst produces O2 at a rate of
more than five catalytic cycles per second.
Hill cautions that many parameters affect
this turnover rate, making it hard to com-
pare catalysts from different labs. But he
believes his cobalt complex is the fastest
known water-oxidation catalyst—1,000
times faster than heterogeneous catalysts
and five times faster than homogeneous
catalysts bearing oxidizable organic ligands.
In a working electrolysis cell, the cata-
lyst could complete a very high number of
turnovers, Hill believes. But it will still be
short of what is needed. Engineers building
solar water-splitting devices say a catalyst
must be able to function for 1 billion turn-
overs to run for several years, he notes.
“Stability is an enormous challenge for the
oxygen-evolving catalyst,” Hill says.
“The focus on purely inorganic catalysts
seems important, because such catalysts
should be more stable over long periods un-
der oxidizing conditions,” observes T. Don
Tilley of the University of California, Berke-
ley, whose group is working on cobalt oxide
nanoparticle electrodes in alkaline solution.
“The work by Nocera has helped to
draw considerable attention to the use of
inorganic catalysts for water splitting and
the fact that such catalysts might be stable
for long periods and over a range of con-
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ditions,” Tilley adds. “Hill’s
work illustrates a new and
different way to utilize purely
inorganic catalysts with
polyoxometalate ligands.
The intriguing thing
about Hill’s catalyst is that
it offers the possibility of
synthetic control over cata-
lyst structure at the molecular
level. The initial results
on these catalysts are
certainly encouraging.”
The biggest challenge for
scientists working on solar fuels
is to start putting together
the components that col-
lect sunlight, split water
to make H2, and supply the H2 to a fuel cell.
“Chemists need to start moving on from
just focusing on making a water-splitting
catalyst to making integrated systems—a
technology,” Nocera says. “It has to be sim-
ple, though, so that it can be manufactured
on a large scale.”
Hill agrees. “A lot of chemists are still in-
terested in modeling enzyme active sites to
study O2 and H2 production mechanisms,”
Hill says. “It’s important research, but it’s
time we go forward with what is working.”
TO THAT END, Sun Catalytix is moving
quickly toward commercialization and
anticipates having its first products ready
in four years, Nocera says. Planned water-
splitting devices to make H2 will use Noce-
ra’s cobalt phosphate water-oxidation cata-
lyst paired with a low-cost water-reduction
catalyst that Sun Catalytix is developing.
One concern is the catalysts’ current
density. Commercial electrolyzers based
on platinum or other costly electrodes
driven by electricity from the power grid to
produce H2 are extremely efficient and op-
erate at current densities as high as 1,000
milliamperes/cm2 to keep the electrodes
at a reasonable size. Nocera’s cobalt phos-
phate catalyst was originally reported to
operate at a current density of 1 mA/cm2,
generating a very small amount of O2. That
value is well below the 40 to 50 mA/cm2
that a solar-powered electrolyzer would
need to generate H2 in full sunlight.
Nocera’s more recent electrodes are op-
erating at about 100 mA/ cm2, he says, which
should be sufficient for what he has in mind.
Nocera envisions developing low-cost “per-
sonalized” energy systems in which rooftop
solar panels supply energy to a home, with
excess energy going to split water in an elec-
28 J U LY 5, 20 10
FAST AND SOLUBLE
Hill’s homogeneous
cobalt polytungstate
molecular water-
oxidation catalyst.
trolyzer to make H2. The
H2 can be temporarily
stored in a tank, Nocera
says, and then used to run an
internal combustion engine
or a fuel cell when the sun
isn’t shining. “Because we are
designing for solar photovolta-
ic input, we don’t need higher
current density,” Nocera says.
Personal-sized electrolyzers
are already available for home use, but No-
cera wants to create one that runs directly
off sunlight and would be affordable to the
20% of the world’s population that has no
regular access to electricity.
Hill is likewise aiming to develop a com-
mercial system. His team’s catalysts are
being patented, Hill says, and he is in dis-
cussion with potential partners whom he
would put in charge of starting a company.
“It’s still too early to think about what type
of commercial applications might be pos-
sible,” he says.
Hill points out that his homogeneous
catalysts would likely have to be tethered
to the electrode surface in a functioning
device. One approach might be to cova-
lently attach the catalyst to light-absorbing
doped titanium dioxide nanoparticles that
can be deposited on the anode surface.
Both Sun Catalytix and Hill’s proposed
new company are coming into existence
at an interesting time. Some experts in the
field are still wondering what the advantag-
es might be to making a better water-split-
ting catalyst and how much better they can
be over current commercial electrolyzers
using precious-metal catalysts. Some sci-
entists contacted by C&EN think Nocera’s
idea of personalized energy is pure folly.
They believe it is more realistic to produce
H2 at large-scale facilities and then generate
the electricity and feed it into a power grid.
Both models for H2 generation may be
viable one day, but many technical hurdles
remain before integrated water-splitting
technology will see wide-scale use. For the
scientists involved, the knowledge that
more energy strikes Earth in one hour from
the sun than is produced from fossil fuels
globally in one year is incentive enough to
continue driving the research forward. ■