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Sunshine in a bottle

Mimic the dance between carbon, hydrogen and oxygen, and you can tap
into clean solar energy and ease climate change
by Peter Forbes

Photo by Jessica Holden/Gallery Stock


Peter Forbes
is a science writer whose work has appeared in New
Scientist, The Guardian, The
Times, Scientific
American and New
Statesman, among others. His latest book, co-authored with Tom Grimsey,
is Nanoscience: Giants of the Infinitesimal (2014). He lives in London.
When I think about the future of renewable energy, I picture the inner
workings of a leaf any leaf. A green plant is a remarkable solar-energy
collector, effortlessly pulling sunlight, water, and carbon dioxide from the
environment, and converting it into stored chemical energy. And the total
amount of energy processed by photosynthesis is enormous. The Sun
bathes the Earth with 173,000 terawatts of solar energy annually. On land
alone, plants convert that energy into more than 100 billion metric tonnes
of biomass. Our global energy use is just 18 terawatts per year, in contrast.
As solar energy proponents are fond of saying: The Sun provides in an hour
enough energy to supply the world for a year.

Humans already have a long tradition of exploiting sunlight trapped by


plants. That is where coal, petroleum and natural gas came from: they are
the fossil remains of ancient biomass, accumulated over many millions of
years. The problem is that burning fossil fuels releases millions of years
worth of carbon dioxide back into the atmosphere all at once. What we
really want to do is replicate the process now, creating new fuel as quickly
as we consume it, with the whole process driven by sunshine. Then we
could bring solar energy to places it has never gone before. We could
provide an unlimited supply of liquid fuels for aircraft and heavy-duty
vehicles such as tractors and trucks, not to mention feedstocks for the
plastics, paints and pharmaceutical industries all with no net carbon
emissions.
The obvious first thought is: why not just let the plants do the work? They
have already mastered the necessary molecular technology. Weve tried
that with biofuels derived from corn, soya, or algae but if we grow crops
like corn for fuel, were robbing the Peter of food production to pay the Paul
of carbon-neutral energy. We could install algal bioreactors in places where
crops cant be grown but then the amounts of water, fertiliser, and energy
consumed in processing the fuel are formidable.
We therefore need to tap the suns energy in a novel, synthetic way. And
that way actually needs to improve on nature, audacious though that
sounds, because the solar energy figures I just mentioned are not quite the
cause for optimism they seem. Natural photosynthesis is only one per cent
efficient. The biomass that became fossil fuels was based on sunlight falling
unhindered on every square centimetre of exposed ground, every second
of every day, for as long as there have been green plants. To make a
meaningful, environmentally sound contribution to the energy supply, we
have to create an industrial process that can make a serious dent in the 36
billion tonnes of CO2 emitted annually by human consumption of fossil
fuels, year in and year out. In other words, we need to do what plants do,
but even better.
Although that sounds daunting, the more we know about natural
photosynthesis, the more we can see that, since it has been cobbled
together piecemeal by evolution, rational design ought to be capable of
improving the yield. The essence of the natural process is to split water to
yield hydrogen and to use the hydrogen to remove the oxygen from CO2 to

make hydrocarbons. What nature accomplishes and what we want to do


is to remove some CO2 from the atmosphere to create biomass. If our
human nanotechnology can mimic that process, we will use up CO2 as
quickly as we produce it. It is almost too elegant that the key ingredient for
addressing climate change could be the substance that is causing the
problem in the first place.
The eventual goal is to obtain the CO2 for fuel production from the
atmosphere itself, but there the CO2 concentration even at its swollen
level of 400 parts per million is impractically low by current industrial
process standards. At present, waste gases from industrial sources such as
coal- and gas-burning power stations, steelworks and cement factories
constitute the best source of CO2 for fuel generation. They also neatly
encapsulate the appeal of liquid solar fuels, as we could transform
smokestack fumes from polluting industries into the raw material for a new
kind of green energy.
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Fortunately, engineers are not heading into entirely uncharted territory.


Chemical reduction of CO2 to make hydrocarbon fuel is already a tried and
tested process. Based on a German invention of 1925, it uses cobalt or iron
catalysts plus energy to make a range of hydrocarbons for fuel, lubricants,
or feedstock. The process has been embraced where economic
circumstances render the extra energy cost acceptable. During the Second
World War, Germany, with no access to oil, used this technology to create
fuel. South Africa today derives about 25 per cent of its fuel by similar
means.
The German process doesnt achieve the desired environmental goals it
actually increases CO2 emissions but it has inspired a promising step
toward true artificial photosynthesis in the hands of George Olah, a
Hungarian-American chemist, now 88 years old. Olahs approach uses
hydrogen produced via renewable electricity in a catalytic process to
reduce CO2 to hydrocarbon or alcohol fuels.

The term reduce has a special meaning in chemistry, and is central both to
the chemistry of life and to the quest for renewable solar fuels. Look around
the countryside on a nice, sunny day and you can see the central chemical
principle of life on Earth. The dense mass of greenery and the blue sky
represents the twin poles of life: oxidation and reduction, or redox. Air in
the sky contains oxygen that liberates energy when it combines with
organic compounds; oxidation is the process that creates fire, and also that
powers your metabolism. The mass of green, on the other hand, is matter
in a chemically reduced state, which is the opposite of what happens in
respiration and combustion. In the presence of oxygen, reduced
compounds can be thought of as having stored energy. Just as oxygen is the
element of oxidation, hydrogen is the element of reduction.
These two elements have been linked in a close dance ever since Earth was
formed, but to complicate matters there is a third partner: carbon. Carbon
can exist in an oxidised state (thats carbon dioxide CO2) or in a reduced
state with hydrogen atoms attached, as in biomass and fuel. All living things
consist of reduced carbon, great long chains and helixes and complicated
clumps of carbon and hydrogen with other key elements attached in
strategic places. Redox reactions the molecular dance between carbon,
hydrogen and oxygen underlie three great mysteries: the origin of life,
how to mitigate global warming, and how to tap the Suns energy without
plants.
The laboratory for Olahs CO2-reducing process is located in Iceland because
of its abundant renewable electricity, generated from that countrys natural
thermal springs. Since 2011, the George Olah Renewable Methanol Plant,
operated near Reykjavik by Carbon Recycling International, has been using
electricity from a thermal power station to split water into water and
hydrogen. A nearby cement works provides a source of waste CO2. The
hydrogen produced by the plant reduces the CO2to methanol. The
methanol (sold by Carbon Recycling International as Vulcanol) can be used
as fuel for vehicles, either straight or mixed with petrol. In July 2015, Carbon
Recycling linked with the UK division of the engineering firm Engie Fabricom
to develop large, standardised CO2-to-methanol plants. Although Icelands
energy situation is unique, George Olah notes that many parts of the world
have access to other forms of cheap renewable electricity (hydropower or
solar-thermal power, for instance) that could drive the plants.

The Olah process is far from artificial photosynthesis, however. Turning


sunlight directly into useful liquid fuels requires understanding the detailed
electro-chemistry of what goes on in green plants, and then learning how
to beat nature at its own game. The details of the photosynthesis process
are immensely complicated: the water-splitting system in plants, called
photosystem II, has two almost identical halves, each of which has 19
protein subunits that use 35 chlorophyll molecules. But at the most basic
level, scientists understand quite well how plants use sunlight to generate
electricity.
Photosynthesis ultimately depends on the photoelectric effect, explained
by Albert Einstein in 1905, in which photons of light interact with electrons,
knocking them free of their atoms. It is the process behind silicon solar
panels. Normally, when sunlight knocks an electron out of any substance,
the electron jumps straight back in. What the natural photosystems do is to
prevent the electrons recombining by smuggling them down a chemical
pathway from which the electron cannot return. A combination of minerals
magnesium in chlorophyll, manganese and calcium in the water-splitting
photocentre and a surrounding protein matrix constrain the electrons so
they have no choice but to be shuffled away.
If our technical catalytic systems fall short of natures, why not just work
with natural organisms?
The task for artificial photosynthesis researchers is to find an equivalent for
the natural pass-the-electron-parcel chains. A lot of the research has
centred on photosystem II, built around an unusually structured group of
manganese, oxygen and calcium atoms (Mn4O5Ca) known as a cubane,
which is embedded in proteins. The bonds between the atoms of cubane
are distorted by the protein matrix; the resulting strain is what enables its
catalytic (reaction-inducing) activity. This manganese, oxygen and calcium
reaction centre is perhaps the chemical crux of life on Earth. But it turns out
that slavishly copying it might not be the best way to create an artificial
photosynthesis system of our own.
Researchers have tried many, many alternatives to the cubane-based
catalyst in green plants, with only limited success. That slow progress has
inspired a whole other approach: if our technical catalytic systems fall short
of natures, why not just work with natural organisms that already have
their own alternatives to green-plant photosynthesis? Weve seen the

drawbacks of using off-natures shelf biomass from corn, soya, or algae, but
could there be a useful halfway point between natural photosynthesis and
a full-blown artificial version? It turn out there is.
There is a group of primitive bacteria the acetogens that can reduce
oxides of carbon without photosynthesis. These microbes perform the
special trick of being able to live off the very gases we are concerned with:
oxides of carbon (carbon monoxide and carbon dioxide), along with
hydrogen. They can generate alcohols from these raw materials and, even
better, can do so using a variety of ratios of hydrogen and carbon
monoxide. This flexibility makes them well-suited for industrial use,
because just such mixtures of gases are produced as the polluting waste
products of electricity generation, as well as steel and cement
manufacture.
LanzaTech, a US energy company devoted to producing liquid fuels from
industrial waste gases, is one of the leading proponents of acetogens. These
ancient bacteria are found naturally today around hydrothermal vents in
the deep ocean, where they live on the hot gases that well up from the
ocean floor. LanzaTech is focusing on one specific bacterium,Clostridium
autoethanogenum, to generate ethanol from waste gases, mostly carbon
monoxide and dioxide from steel mills.
Jennifer Holmgren, LanzaTechs CEO, recognises that having a clever idea is
not enough if you are trying to shift the enormous fossil-fuel industry.
Scaling up is the most important thing for any new technology, she says.
If it doesnt scale, it doesnt matter. To that end, the company has created
a demonstration plant at the Baosteel mill in Shanghai, China, and last year
they signed an agreement with the worlds biggest steelmakers,ArcelorMittal, to build a 87 million fuel-generating plant at their
Ghent steelworks in Belgium. LanzaTech has also signed a deal to supply
Virgin Atlantic with bio-aviation fuel.
This last venture touches on one of Holmgrens key concerns, bringing
carbon reductions to the parts of the energy economy that green electricity
cannot easily reach. If we go to electric vehicles on a large scale, how do
we balance the system? she asks. The system requires production of
fuels ground and aviation and chemical coproducts. If the ground fuels
portion goes off to electric, lets say 30 per cent of ground transport, what
happens to the economics of aviation fuel and chemicals production?

LanzaTechs approach is an important step toward true artificial


photosynthesis, since it yields biofuels without relying on the usual green
plants, but it is still only a beginning. More far-reaching are the experiments
now underway to develop hybrid fuel-production systems ones that still
exploit energy-harvesting mechanisms found in nature, but that add
synthetic components to make them serve our needs more effectively.
This work has been greatly aided by the remarkable discovery that some
bacteria can live directly off a diet of electricity. Peidong Yang, a Chineseborn professor of chemistry at the University of California, Berkeley, has
exploited this appetite for electrons by matching the bacteria with
microscopic semiconductors that act as tiny solar cells. The bacteria grab
electrons from the semiconductors and use them to reduce CO2. Its a
brilliant synthesis: semiconductors are the most efficient light harvesters,
and biological systems are the best scavengers of CO2.
Methane is not a liquid fuel, but it can readily be converted to one. It can
also be used directly as natural gas to run power plants
Yangs team is currently studying three different systems. In one, the
researchers built a forest of silicon and titanium dioxide nano-wires as the
light harvester, and then cultured the bacterium Sporomusa ovata to grow
over the wires and feed on the electricity. In another system, the
researchers precipitated light-harvesting cadmium sulphide nanoparticles
onto Moorella thermoacetica; the particles enable the previously nonphotosynthetic bacteria to turn light, water and CO2 into acetic acid, which
can readily be transformed into fuels such as butanol, or synthesised into
plastics and pharmaceuticals. It is artificial photosynthesis in a truly
profound way, bringing the photosynthetic ability to an organism that never
had it for billions of years.
The third method is the most conventional, but it also looks like the most
likely one to scale up. Combining an electrochemical cell (driven by
electricity, sunlight, or a combination of the two) with the bacterium
(Methanosarcina barkeri) produces methane with an impressive 10 per
cent solar-to-fuel conversion rate. Methane is not a liquid fuel, but it can
readily be converted to one. It can also be used directly as natural gas to
run power plants. This approach could solve one of renewable energys
most pressing problems. Electricity cannot be easily stored, and both sun
and wind are powerful but intermittent energy sources. Solar-generated

methane can be stored to provide electricity generation when the sun


doesnt shine and the wind doesnt blow.
Unlike natural photosynthesis, all of these artificial systems at present
require concentrated CO2 to work. Ideally wed be working with 400 ppm
[parts per million] CO2 in the atmosphere, but no one knows how to do that
yet, no one, Yang says. There is an upside, though. The current approaches
can be readily coupled with carbon-capture technology to pull CO2 from
smokestack emissions and convert it into fuel. This is the essential element
of a closed carbon cycle that mimics nature, consuming the carbon created
by human industry rather than dumping it into the environment. But that
cycle still ultimately depends on the presence of the polluting industries.
Then again, we do now know how to use CO2 drawn directly from the air,
on a laboratory scale at least. In January this year, George Olahs group at
the University of Southern California reported dramatic new work. Olahs
colleague G K Surya Prakash along with the PhD student Jotheeswari
Kothandaraman have developed a combined process that uses a polyamine
(a class of organic molecules essential both to life and to many industrial
chemical processes) to capture carbon dioxide from the atmosphere, in
conjunction with a ruthenium-based catalyst to reduce the CO2 to
methanol. Ruthenium catalysts have been employed before to reduce
carbon dioxide, but making the process work at atmospheric levels of CO2,
in a unified process with the carbon-capturing reaction, is a notable
advance. In tests, up to 79 per cent of the CO2 captured from the air was
converted into methanol.
The Olah group have been pursuing their vision of a methanol economy
for many years and, with their experience from the Carbon Recycling plant
in Iceland, they are well-placed to figure out how to make it work in a
commercially viable way. Doing so will involve juggling a bewildering array
of processes and market variables, though. Large-scale capture of
atmospheric CO2 would require prodigious quantities of polyamine, which
raises issues of environmental safety. Ruthenium is a rare-earth metal that
has seen considerable volatility in supply and cost. Its current price is
around $42 per ounce, but a decade ago the price was more than $850.
These challenges should not deter us. We have grown used to accepting
that we have to follow wherever the market leads us, which is how fossil
fuels have remained so entrenched in the global economy for so long. But

today there are bigger concerns than short-term market efficiency. We


must have a reliable, secure, long-term, carbon-neutral fuel supply. That is
the cornerstone of our future energy needs, and the other arrangements
will have to be fitted around it.
Carbon is precious. We must learn to recycle it. There should be no waste.
There is no waste in nature
Back in 2008, the photosynthesis expert James Barber of Imperial College
London advocated an Apollo-style programme, comparable in scale and
urgency to the 1960s Moon race, to develop solar fuels. Its taken a while,
but their call is finally being heeded. Once the least known of renewable
energy technologies, solar liquid fuels now have powerful advocates. In
particular, Bill Gates recently organised the Breakthrough Energy Coalition,
a group of 28 investors aiming to boost world spending on carbon-free
energy development to $20 billion a year. He also catalysed Mission
Innovation, a 20-major-nation governmental initiative launched at the Paris
climate change conference in December 2015.
Gates has some powerful advantages. He understands both the
technological and financial challenges, and has plenty of financial resources
himself, having pledged $2 billion to the project. His thinking is outlined in
a paper, Energy Innovation: Why we need it and how to get it. The US
government is also getting on board with the new approach. In April 2015,
the Department of Energys Joint Center for Artificial Photosynthesis (JCAP)
announced renewed funding of $75 million and a change of direction, away
from hydrogen production and toward the kind of solar-generated liquid
fuels Ive been describing. With researchers, foundations, major world
governments, and large investors all pulling in the same direction, success
is looking far more probable that it did just a couple years ago although,
as Gates points out, such major technological shifts have typically taken
decades in the past. At the same time, programs like JCAP are puny
compared to the total magnitude of the R&D effort needed.
The costs are high, but the potential payoff is even higher. Holmgren at
LanzaTech lays out a compelling vision: Carbon is precious. This means we
must learn to recycle it. If you can extend its life by reusing it in a fuel, you
will keep that equivalent amount of fossil fuel in the ground. There should
be no waste. There is no waste in nature.

Redox reactions the dance between carbon, hydrogen, and oxygen


produced the cornucopia of life on Earth. Right now, we are merely running
down those reactions, unwinding millions of years of biochemistry that is
locked away in the planets fossil fuels, and systematically polluting the
atmosphere in the process. We need to understand the redox reactions, so
we can master the biomechanical machinery of photosynthesis and start
building up with it. Success could transform the world economy, and the
global environment. It is a challenge we cannot afford to pass up.